Alkanoyl anilides

ABSTRACT

The present invention is in alkanoyl anilides exhibiting insecticidal and arachnicidal activity, wherein the alkanoyl is both branched and substantially or totally fluorinated.

CROSS REFERENCE TO RELATED APPLICATION

This is a division of my copending application Ser. No. 06/836,658, filed Mar. 5, 1986, which is in turn U.S. Pat. No. 4,826,841 a continuation-in-part of my copending application Ser. No. 720,236 filed Apr. 5, 1985 and abandoned after the filing of application Ser. No. 06/836,658.

BRIEF SUMMARY OF THE INVENTION

The present invention is in alkanoyl anilides of which the alkanoyl is both branched and substantially or totally fluorinated. These anilides exhibit excellent insecticidal and arachnicidal activity. The invention therefore also includes methods employing, and formulations comprising, these compounds as insecticides and arachnicides. The novel alkanoyl anilides are defined by the following formulae ##STR1## wherein R⁰ represents

bromo,

chloro, or

fluoro;

R¹ represents

CF₃,

C₂ F₅,

C₃ F₇, or

a n-, iso-, or sec-C₄ F₉ ;

R² represents

CF₃, C₂ F₅, C₃ F₇, or,

when R⁰ represents fluoro, R² can additionally represent

--OR_(f),

--N(R_(f))₂,

--CN,

--CF₂ --OR_(f), or

--CF₂ --N(R_(f))₂

and each R_(f) independently represents perfluoroloweralkyl of C₁ -C₄ or, in --N(R_(f))₂ both R_(f) groups can be taken together with the N and constitute perfluoropyrrolidino, perfluoropiperidino, perfluoromorpholino, or N-(trifluoromethyl)perfluoropiperazino;

R³ represents

hydrogen, or

methyl; and

R⁴ represents

5-nitro-2-pyridyl,

thiocyanatophenyl bearing a single additional substituent which is fluoro, chloro, bromo, iodo, or nitro, or

substituted aryl of the formula ##STR2## wherein each R⁵ independently represents bromo,

chloro, or

fluoro;

each R⁶ independently represents

iodo,

nitro,

cyano,

trifluoromethyl,

fluorosulfonyl,

methylsulfonyl,

ethylsulfonyl,

carbomethoxy, or

carboethoxy;

R⁷ represents

methyl, or,

when two R⁶ moieties represent nitro at the 2-and 4-positions, R⁷ can additionally represent C₁ -C₄ alkoxy or C₁ -C₄ alkylthio located at only the 3- or 5-position;

n represents 0-5; p represents 0-2 except that p can additionally represent 3 but only where two R⁶ moieties represent nitro and a third R⁶ moiety represents trifluoromethyl; q represents 0, or, when at least one R⁵, nitro, or fluorosulfonyl group is present, 1; r represents 0 or 1; and the sum of n, p, and q is:

2-5 when each of p, q, and r is 0;

2-3 when any one of p, q, or r is at least 1, except that when p is one and R⁶ is 4-nitro, the sum of n and p can additionally be 1;

or a sodium, potassium, or ammonium salt of a foregoing compound, wherein ammonium is of the following formula ##STR3## wherein each R⁸ independently represents alkyl of C₁ -C₂₀, benzyl, 2-hydroxyethyl, 2-hydroxypropyl, or 3-hydroxypropyl; and R⁹ represents hydrogen or R⁸, the total number of carbon atoms in all R⁸ and R⁹ moieties being from 12 to 60, except that when one or more R⁸ groups are 2-hydroxyethyl, 2-hydroxypropyl, or 3-hydroxypropyl, the total number of carbon atoms in all R⁸ and R⁹ moieties can be from 6 to 60.

DETAILED DESCRIPTION OF THE INVENTION Synthesis

The present compounds are prepared in conventional procedures for the preparation of carboxanilides. A preferred method is the reaction of the appropriate alkanoyl halide: ##STR4## with the desired aniline, 1-aminonaphthalene, or 2-amino-5-nitropyridine, of the formula ##STR5## Preferably the halide is fluoride. In carrying out this reaction, the reactants are combined in a reaction solvent. Various solvents can be employed, including toluene, acetonitrile, diethyl ether, tetrahydrofuran, and halogenated solvents such as methylene chloride. In general, diethyl ether and halogenated solvents are preferred. A halogenated solvent can sometimes serve as the solvent in a "one-pot" reaction to make the starting material which is thereafter converted to the final product of the invention. In other particulars, the reaction is conventional. An HF acceptor is provided to the reaction mixture; typically triethylamine is used. The reaction consumes the reactants and the HF acceptor in equimolar amounts. The reaction goes forward over a wide temperature range, such as from 10° to 110° C.; however, the reaction is most conveniently carried out at temperatures of about 20° to 70° C. Workup of the reaction mixture to isolate the product is carried out in conventional procedures.

The alkanoyl halides employed as starting materials in this reaction route are generally prepared by electrochemical fluorination and therefore often contain isomers. In view of the requirement of the present invention for branching alpha to the carbonyl, it is often desirable to purify the anilide products to remove straight-chain isomers. It has been found that this can generally be achieved by selective hydrolysis of the straight-chain carboxanilides, and separation of the water soluble K or Na salt of the branched chain carboxanilide from the precipitated aniline. This is illustrated by Examples 2, 3, 8, and 13 below.

An alternate procedure is available for the preparation of those compounds of formula I wherein R⁰ represents fluoro, both R¹ and R² represent trifluoromethyl, and R³ represents hydrogen; however, this procedure is less favored than the proceeding one. The procedure involves the reaction of an olefin, hexafluoropropene, and an isocyanate in the presence of a fluoride such as KF, NaF, or cesium fluoride: ##STR6## The reaction is carried out in a reaction solvent such as DMF, DMSO, or diglyme, under pressure of 5-40 psig. The reaction goes forward over a range of temperatures, such as from 30° to 70° C. The reaction requires one mole of isocyanate, three or more moles of KF, NaF, or cesium fluoride, and three to ten or more moles of hexafluoropropene. Workup is conventional.

Those compounds of the present invention in which R³ represents methyl are preferably prepared from the corresponding R³ =hydrogen compounds. This methylation reaction is carried out in any of the known conventional methods for methylation. Typically, methyl iodide is employed as the reagent, and the reaction is carried out in a suitable solvent, such as acetone, with a base such as potassium carbonate. Equimolar amounts of the reactants are consumed, but the methyl iodide is preferably used in excess. The reaction goes forward over a wide range of temperatures, but is most conveniently carried out at room temperatures of about 25° to 35° C. Workup is by conventional procedures.

The present invention also includes salts of the parent compounds. These salts are prepared in entirely conventional methods. The sodium and potassium salts are prepared by reacting the corresponding parent compounds with sodium or potassium hydroxide; the ammonium salts can be obtained by reacting the parent compound with a compound of the formula ##STR7## or by reacting a sodium salt of a present compound with ##STR8##

The synthesis of the present compounds is further taught by the following illustrative examples.

EXAMPLE 1 2'-Bromo-4'-nitor-2,3,3,3-tetrafluoro-2-(trifluoromethy)propionanilide (olefin process)

Potassium fluoride (23 grams; 0.4 mole) which was dried by heating strongly with a bunsen burner in a porcelain crucible and subsequently powdered, was added to 200 ml of a DMF solution of 2-bromo-4-nitrophenyl isocyanate (6 grams; 0.025 mole). The mixture was placed in a pressure vessel, purged with a small stream of hexafluoropropene, and heated to 70° C. while adding hexafluoropropene from a pre-weighed supply cylinder at 10-20 psig. A pressure drop occurred as the gas reacted, and the remaining hexafluoropropene was added intermittently until the supply cylinder was empty; heating was continued at 65°-70° C. for 21/2 hours with pressure stabilized at 5 psig. The reaction vessel was then cooled and the solution poured off and extracted with hexane. The DMF solution was poured into water and filtered. The solid products were taken up in chloroform, dried over sodium sulfate, filtered, evaporated, and chromatographed on silica gel with ethyl acetate/ hexane (1:5). The front-running product was collected; H-NMR of this product indicated the desired product. The material was then chromatographed on silica gel with gradient elution from 100% hexane to 100% ethyl acetate.

The foregoing procedures yielded a waxy solid, m.p. 57°-59° C., yield 1.65 grams (16%). The identity of the product was confirmed by MS, H-NMR, and F¹⁹ -NMR

Analysis calculated for C₁₀ H₄ BrF₇ N₂ O₃ :

Theory: C, 29.08; H, 0.98; N, 6.78;

Found: C, 29.31; H, 0.83; N, 6.58.

EXAMPLE 2 2'-Bromo-4'-nitro-2,3,3,3-tetrafluoro-2-(trifluoromethyl)propionanilide (alkanoyl fluoride process, with isomer purification)

2-Bromo-4-nitroaniline (141 grams; 0.65 mole) was dissolved in 3.5 liters of diethyl ether, dried over sodium sulfate, and filtered. Triethylamine (71 grams; 0.070 mole) was added with stirring. A mixture of 2,2,3,3,4,4,4-heptafluorobutyryl fluoride, 2,3,3,3-tetra-fluoro-2-(trifluoromethyl)propionyl fluoride, HF, and inert gases were employed The mixture was believed to contain 70% of chemically active acyl fluorides; 100 grams of this mixture were add under a dry ice/acetone condensor. The reaction mixture was left to stand overnight (about 17 hours) and an additional amount of the mixture was added to a total of 210 grams (0.70 mole).

Water was added to the reaction mixture, then dilute ice/HCl until the pH of the aqueous layer was acidic. The water layer was decanted off. The diethyl ether layer was dried over magnesium sulfate and the solvent evaporated under vacuum.

The solid residue was taken up in 800 ml of ethanol, and treated with potassium carbonate at room temperature, with magnetic stirring. Sixty-eight grams of K₂ CO₃ was added initially, followed by 23 g more after 24 hours and 12 g more after 48 hours and stirred for a total of 64 hours. The ethanol was evaporated under vacuum, and the solids were triturated three times with aqueous potassium carbonate. The solution was filtered and the filtrate was acidified below 25° C. with HCl. The product was filtered, washed with water, dissolved in methylene chloride, dried, and evaporated. The gas chromatogram of the product indicated less than 1% straight-chain isomer, m.p., 66° C., yield, 178 grams (66%).

Analysis calculated for C₁₀ H₄ BrF₇ N₂ O₃ :

Theory: C, 29.08; H, 0.98; N, 6.78;

Found: C, 29.30; H, 0.92; N, 6.99.

EXAMPLE 3 2'-Bromo-4'-nitro-2,3,3,3-tetrafluoro-2(trifluoromethyl)propionanilide (alkanoyl fluoride process, with isomer purification)

2-Bromo-4-nitroaniline (35.84 grams; 0.16 mole), triethylamine (21.15 grams; 0.21 mole), and 250 ml of tetrahydrofuran were added to a 500 ml roundbottom flask equipped with a dry ice/acetone reflux condenser and a gas inlet. The vessel was purged with nitrogen. The same mixture of acyl fluorides used in Example 2 was employed as the reactant in the present example (54.60 grams; 0.18 mole). This mixture was added at a rate allowing a slow reflux. The addition required approximately 90 minutes and the resulting brown solution was stirred for about an hour after the addition was complete.

The reaction mixture was then washed with 60 ml of a 50/50 mixture of water/saturated sodium chloride solution and 40 ml of saturated sodium chloride solution. The aqueous layers were discarded.

One hundred fifty milliliters of 1N sodium hydroxide was then added to the organic layer and 90 ml of volatile material was distilled off at atmospheric pressure. Another 100 ml of 1N sodium hydroxide was added to the solution, and the resulting solution was distilled until the head temperature rose above the boiling point of tetrahydrofuran, 66° C. The pot temperature was held constant until HPLC confirmed the hydrolysis of the straight-chain product by the basic solution. The resulting aniline precipitated out at this time and was removed by filtration.

The filtrate was allowed to cool, then washed twice, with 150 ml and 100 ml of methylene chloride. The aqueous layer was separated and placed under vacuum to remove any residual organic solvents. The solution was then placed in an ice bath and the pH was lowered to 7 with concentrated hydrochloric acid. The desired 2'-bromo-4'-nitro-2,3,3,3-tetrafluoro-2-(trifluoromethyl)propionanilide precipitated and was separated by filtration, washed with distilled water, and dried overnight in vacuo at room temperature, 42.95 grams (86.0%) in 99.5% purity by HPLC.

Other compounds of the present invention were prepared by the alkanoyl fluoride procedure except where noted otherwise. Preparations by the alkanoyl fluoride process were isolated as isomer mixtures except as noted in Examples 8 and 13.

These other compounds of the present invention are listed in the following Examples. In each example, the identity of the product was confirmed by H-NMR. The percentage of the desired branched chain isomer in the product, as determined by F¹⁹ -NMR, is also reported.

EXAMPLE 4

2,-Cyano-4'-nitro-2,3,3,3-tetrafluoro-2-(trifluoromethyl)propionanilide, m.p., 100°-101° C., yield 50% (72% branched isomer).

Analysis calculated for C₁₁ H₄ F₇ N₃ O₃ :

Theory: C, 36.79; H, 1.12; N, 11.70;

Found: C, 37.05; H, 1.22; N, 11.89.

EXAMPLE 5

2'-Methyl-4'-nitro-2,3,3,3-tetrafluoro-2-(trifluoromethyl)propionanilide, m.p., 120°-122° C., yield 22% (93% branched isomer).

Analysis calculated for C₁₁ H₇ F₇ N₂ O₃ :

Theory: C, 37.95; H, 2.03; N, 8.05;

Found: C, 38.10; H, 1.95; N, 8.26.

EXAMPLE 6

2'-(trifluoromethyl)-4'-nitro-2,3,3,3-tetrafluoro-2-(trifluoromethyl)propionanilide, m.p., 53°-54° C., yield 15% (>95% branched isomer).

Analysis calculated for C₁₁ H₄ F₁₀ N₂ O₃ :

Theory C, 32.85; H, 1.00; N, 6.97;

Found: C, 32.79; H, 1.15; N, 7.01.

EXAMPLE 7

2',3',4',5',6',2,3,3,3-Nonafluoro-2-(trifluoromethyl)propionanilide, m.p., 137°-142° C., yield 85% (60% branched isomer)

Analysis calculated for C₁₀ HF₁₂ NO:

Theory: C, 31.68; H, 0.27; N, 3.69;

Found: C, 31.42; H, 0.23; N, 3.89.

EXAMPLE 8

2'-Chloro-4'-nitro-2,3,3,3-tetrafluoro-2(trifluoromethyl)propionanilide, m.p., 52°-53° C., yield 94% (86% branched isomer).

Analysis calculated for C₁₀ H₄ ClF₇ N₂ O₃ :

Theory: C, 32.59; H, 1.09; N, 7.60;

Found: C, 32.82; H, 0.97; N, 7.63.

This product was purified by treatment with potassium carbonate ethanol, as follows. The product (4 grams; 0.0108 mole) was dissolved in 20 ml of 95% ethanol and potassium carbonate (1.1 gram; 0.008 mole) was added. The mixture was maintained for 5 days at room temperature The ethanol was then evaporated off at room temperature. Potassium carbonate (1.1 gram) in 50 ml of water was added at 40° C. with vigorous stirring. The mixture was filtered and washed with 40° C. water. The filtrate was cooled, acidified with HCl, filtered, and air dried, yielding 2.8 grams (70% yield) of purified product melting at 67° C. The gas chromatogram and F¹⁹ -NMR confirmed that the product was >99% branched isomer.

EXAMPLE 9

2',3',4',6',2,3,3,3-Octafluoro-2-(trifluoromethyl)propionanilide, m.p., 104°-108° C., yield 31% (78% branched isomer).

Analysis calculated for C₁₀ H₂ F₁₁ NO:

Theory: C, 33.26; H, 0.56; N, 3.88;

Found: C, 33.54; H, 0.78; N, 3.94.

EXAMPLE 10

2',4',5'-Trichloro-2,3,3,3-tetrafluoro-2(trifluoromethyl)propionanilide, m.p., 69°-72° C., yield 55% (87% branched isomer).

Analysis calculated for C₁₀ H₃ Cl₃ F₇ NO:

Theory: C, 30.60; H, 0.77; N, 3.57;

Found: C, 30.69; H, 1.01; N, 3.62.

Another preparation of the same compound was made, m.p., 80°-81° C., yield 67% (91% branched isomer).

Found: C, 30.47; H, 1.04; N, 3.43.

EXAMPLE 11

2',3',5',6',2,3,3,3-Octafluoro-2-(trifluoromethyl)propionanilide, m.p., 94°-99° C., yield 69% (82% branched isomer).

Analysis calculated for C₁₀ H₂ F₁₁ NO:

Theory: C, 33.26; H, 0.56; N, 3.88;

Found: C, 33.06; H, 0.34; N, 4.00.

EXAMPLE 12

2',3',4',5!-Tetrachloro-2,3,3,3-tetrafluoro-2-(trifluoromethyl)propionanilide, m.p., 82°-83° C., yield 18% (95% branched isomer).

Analysis calculated for C₁₀ H₂ Cl₄ F₇ NO:

Theory: C, 28.13; H, 0.47; N, 3.28;

Found: C, 28.35; H, 0.52; N, 3.30.

EXAMPLE 13 Preparation #1

2',5'-Dichloro-4'-nitro-2,3,3,3-tetrafluoro-2-(trifluoromethyl)propionanilide was prepared by the olefin procedure, m.p. 80°-82° C., yield 12% (>99% branched isomer).

Analysis calculated for C₁₀ H₃ Cl₂ F₇ N₂ O₃ :

Theory: C, 29.80; H, 0.75; N, 6.95;

Found: C, 29.90; H, 0.53; N, 6.98.

Preparation #2

2',5'-Dichloro-4'-nitro-2,3,3,3-tetrafluoro-2-(trifluoromethyl)propionanilide was also prepared by the alkanoyl fluoride procedure, m.p., 81°-83° C., yield 47% (94% branched isomer). Microanalysis showed

Found: C, 30.07; H, 0.53; N, 6.92.

This product was purified by treatment with potassium carbonate, as described above in Example 8, m.p. 83°-85° C., yield 82% of >99% branched isomer.

EXAMPLE 14

2',3'-Dichloro-2,3,3,3-tetrafluoro-2-(trifluoromethyl)propionanilide, m.p., 71°-73° C., yield 32% (99.4% branched isomer).

Analysis calculated for C₁₀ H₄ Cl₂ F₇ NO:

Theory: C, 33.55; H, 1.13; N, 3.91;

Found: C, 33.59; H, 1.25; N, 3.95.

EXAMPLE 15

N-(5-Nitro-2-pyridyl)-2,3,3,3-tetrafluoro-2-(trifluoromethyl)propionamide, m.p., 75°-77° C., yield 42% (97% branched isomer).

Analysis calculated for C₉ H₄ F₇ N₃ O₃ :

Theory: C, 32.26; H, 1.20; N, 12.54;

Found: C, 32.19; H, 1.00; N, 12.45.

EXAMPLE 16 2',6'-Dichloro-4'-nitro-2,3,3,3-tetrafluoro-2-(trifluoromethyl)propionanilide, m.p., 128°-134° C., yield 13% (59% branched isomer).

Analysis calculated for C₁₀ H₃ Cl₂ F₇ N₂ O₃ :

Theory: C, 29.80; H, 0.75; N, 6.95;

Found: C, 29.84; H, 0.97; N, 7.09.

EXAMPLE 17

2'-Methyl-4'-nitro-5'-chloro-2,3,3,3-tetra- fluoro-2-(trifluoromethyl)propionanilide, m.p., 114°-116° C., yield 53% (91% branched isomer).

Analysis calculated for C₁₁ H₆ ClF₇ N₂ O₃ :

Theory: C, 34.53; H, 1.58; N, 7.32;

Found: C, 34.40; H, 1.61; N, 7.31.

EXAMPLE 18

2',4',6'-Trichloro-2,3,3,3-tetrafluoro-2(trifluoromethyl)propionanilide, m.p., 133°-135° C., yield 33% (87% branched isomer).

Analysis calculated for C₁₀ H₃ Cl₃ F₇ NO:

Theory: C, 30.60; H, 0.77; N, 3.57;

Found C, 30.47; H, 0.92; N, 3.47.

EXAMPLE 19

3',4',5'-Trichloro-2,3,3,3-tetrafluoro-2-(trifluoromethyl)propionanilide, m.p., 145°-146° C., yield 38% (95% branched isomer).

Analysis calculated for C₁₀ H₃ Cl₃ F₇ NO:

Theory: C, 30.60; H, 0.77; N, 3.57;

Found: C, 30.82; H, 1.06; N, 3.50.

EXAMPLE 20

2'-Chloro-5'-nitro-2,3,3,3-tetrafluoro-2-(trifluoromethyl)propionanilide, m.p., 68°-70° C., yield 35% (84% branched isomer).

Analysis calculated for C₁₀ H₄ F₇ N₂ O₃ :

Theory: C, 32.59; H, 1.09; N, 7.60;

Found: C, 32.64; H, 1.33; N, 7.49.

EXAMPLE 21

2',4'-Dinitro-2,3,3,3-tetrafluoro-2-(trifluoromethyl)propionanilide, m.p., 50°-51° C., yield 21% (85% branched isomer).

Analysis calculated for C₁₀ H₄ F₇ N₃ O₅ :

Theory: C, 31.68; H, 1.06; N, 11.08;

Found: C, 31.42; H, 1.15; N, 10.84.

EXAMPLE 22

2'-Iodo-4'-nitro-2,3,3,3-tetrafluoro-2-(trifluoromethyl)propionanilide, m.p., 107°-110° C., yield 8% (39% branched isomer).

Analysis calculated for C₁₀ H₄ IF₇ N₂ O₃ :

Theory: C, 26.11; H, 0.88; N, 6.09;

Found: C, 26.28; H, 1.11; N, 5.90.

EXAMPLE 23

2'-Cyano-4'-chloro-2,3,3,3-tetrafluoro-2-(trifluoromethyl)propionanilide, m.p., 90°-91° C., yield 5% (91% branched isomer).

Analysis calculated for C₁₁ H₄ ClF₇ N₂ O:

Theory: C, 37.90; H, 1.16; N, 8.04;

Found: C, 38.08; H, 1.10; N, 7.84.

EXAMPLE 24 2'-Bromo-4'-nitro-2,3,3,3-tetrafluoro-2-(trifluoromethyl)propionanilide, tetra-n-propyl-ammonium salt

2'-Bromo-4'-nitro-2,3,3,3-tetrafluoro-2-(trifluoromethyl)propionanilide, (20 grams of material free of straight-chain isomer; 0.048 mole) was dissolved in 200 ml of acetone. The solution was maintained at room temperature while 2N sodium hydroxide (25 ml; 0.05 mole) and tetra-n-propylammonium bromide (13.5 grams 0.051 mole) were added. The reaction mixture was stirred for 45 minutes, evaporated at room temperature, and partitioned between methylene chloride/water. The organic phase was washed twice with water, dried over sodium sulfate, and evaporated to dryness, yielding 28.7 grams of the intended salt (99% yield). The identity of the product was confirmed by H-NMR. The product solidified upon standing, m.p., 57°-65° C.

Analysis calculated for C₂₂ H₃₁ BrF₇ N₃ O₃ :

Theory: C, 44.16; H, 5.22; N, 7.02;

Found: C, 44.14; H, 5.05; N, 6.80.

A second preparation was conducted similarly, and the identity of the product was confirmed by H-NMR. The yield was 9.2 grams (91%), m.p. 72°-75° C.

Found: C, 43.88; H, 4.50; N, 6.83.

A third preparation was similarly conducted, except the starting anilide was only 86% of the desired 2'-bromo-4'-nitro-2,3,3,3-tetrafluoro-2-(trifluoromethyl)propionanilide, the remaining 14% being the corresponding straight-chain isomer. The product of this reaction was an oil. The identity was confirmed by H-NMR.

Found: C, 44.02; H, 5.07; N, 7.02.

Other salts were prepared in similar manner and are reported below. In each preparation, the identity of the product was confirmed by H-NMR. The starting anilide in these preparations, and therefore the corresponding salt as well, was either essentially pure 2'-bromo-4'-nitro-2,3,3,3-tetrafluoro-2-(trifluoromethyl)propionanilide (referred to as "isomer pure") or a mixture of 86% of this compound and 14% of the corresponding straight-chain isomer (referred to as "86% isomer").

EXAMPLE 25

2'-Bromo-4'-nitro-2,3,3,3-tetrafluoro-2-(trifluoromethyl)propionanilide, tetraethylammonium salt, monohydrate, m.p., 112° C., yield 60% (isomer pure).

Analysis calculated for C₁₈ H₂₅ BrF₇ N₃ O₄ :

Theory: C, 38.59; H, 4.50; N, 7.50;

Found: C, 38.85; H, 4.25; N, 7.48.

EXAMPLE 26

2'-Bromo-4'-nitro-2,3,3,3-tetrafluoro-2-(trifluoromethyl)propionanilide, tetra-n-butylammonium salt, monohydrate, m.p., 78°-80° C., yield 66% (isomer pure).

Analysis calculated for C₂₆ H₄₁ BrF₇ N₃ O₄ :

Theory: C, 46.44; H, 6.14; N, 6.25;

Found: C, 46.66; H, 6.29; N, 6.12.

EXAMPLE 27

2'-Bromo-4'-nitro-2,3,3,3-tetrafluoro-2-(trifluoromethyl)propionanilide, tetra-n-pentylammonium salt, monohydrate.

Preparation #1, m.p., 55°-57° C., yield 80% (isomer pure).

Analysis calculated for C₃₀ H₄₉ BrF₇ N₃ O₄ :

Theory: C, 49.45; H, 6.73; N, 5.77;

Found: C, 50.80; H, 6.93; N, 5.69.

F84-1N9-277

Preparation #2, m.p., 54°-56° C., yield 76% (86% isomer)

EXAMPLE 28

2'-Bromo-4'-nitro-2,3,3,3-tetrafluoro-2-(trifluoromethyl)propionanilide, tetra-n-heptylammonium salt, monohydrate, an oil, yield 50% (isomer pure).

Analysis calculated for C₃₈ H₆₅ BrF₇ N₃ O₄ :

Theory: C, 54.28; H, 7.79; N, 5.00;

Theory*: C, 54.47; H, 7.66; N, 5.11;

Found: C, 56.27; H, 8.68; N, 4.59.

EXAMPLE 29

2,-Bromo-4'-nitro-2,3,3,3-tetrafluoro-2-(trifluoromethyl)propionanilide, methyltri-n-octylammonium salt, monohydrate, an oil, yield 70% (86% isomer.

Analysis calculated for C₃₅ H₅₉ BrF₇ N₃ O₄ :

Theory: C, 52.11; H, 7.20; N, 5.36;

Found: C, 52.63; H, 7.39; N, 5.26.

EXAMPLE 30

2'-Bromo-4'-nitro-2,3,3,3-tetrafluoro-2-(trifluoromethyl)propionanilide, methyltris(C₈ -C₁₀)-ammonium salt, monohydrate, an oil, yield 60% (86% isomer.

EXAMPLE 31

2'-Bromo-4'-nitro-2,3,3,3-tetrafluoro-2-(trifluoromethyl)propionanilide, hexadecyltrimethylammonium salt, monohydrate.

Preparation #1, an oil, yield 48% (isomer pure).

Analysis calculated for C₂₉ H₄₇ BrF₇ N₃ O₄ :

Theory: C, 48.74; H, 6.63; N, 5.88;

Found: C, 49.03; H, 6.39; N, 5.78.

Preparation #2, an oil, yield 6% (86% isomer).

Found: C, 47.54; H, 6.09; N, 5.90.

EXAMPLE 32

2'-Bromo-4'-nitro-2,3,3,3-tetrafluoro-2-(trifluoromethyl)propionanilide, octadecyltrimethylammonium salt, m.p., 45°-48° C., yield 52% (86% isomer).

Analysis calculated for C₃₁ H₄₉ BrF₇ N₃ O₃ :

Theory: C, 51.38; H, 6.76; N, 5.80;

Found: C, 52.03; H, 6.67; N, 5.67.

EXAMPLE 33

2'-Bromo-4'-nitro-2,3,3,3-tetrafluoro-2-(trifluoromethyl)propionanilide, benzyltri-n-butylammonium salt, monohydrate, an oil, yield 14% (86% isomer).

Analysis calculated for C₂₉ H₃₉ BrF₇ N₃ O₄ :

Theory: C, 49.30; H, 5.56; N, 5.95;

Found: C, 50.21; H, 5.96; N, 5.64.

EXAMPLE 34

2'-Bromo-4'-nitro-2,3,3,3-tetrafluoro-2-(trifluoromethyl)propionanilide, dimethylbis)ammonium salt, monohydrate, m.p., 65°-70° C., yield 48% (86% isomer).

EXAMPLE 35

2'-Bromo-4'-nitro-2,3,3,3-tetrafluoro-2-(trifluoromethyl)propionanilide, dimethylbis(C₁₀ -C₁₈)-ammonium salt, an oil, yield 42% (isomer pure).

EXAMPLE 36

2'-Bromo-4'-nitro-2,3,3,3-tetrafluoro-2-(trifluoromethyl)propionanilide, dimethylbis (C₁₄ -C₁₈)-ammonium salt, monohydrate, an oil, yield 45% (86% isomer).

EXAMPLE 37

2'-Bromo-4'-nitro-2,3,3,3-tetrafluoro-2-(trifluoromethyl)propionanilide, tributylammonium salt, m.p., 58°-60° C., yield 87% (isomer pure).

Analysis calculated for C₂₂ H₃₁ BrF₇ N₂ O₃ :

Theory: C, 44.15; H, 5.18; N, 7.02;

Found: C, 43.27; H, 3.47; N, 6.96.

Except where noted otherwise, the following additional examples were prepared by the foregoing procedures.

EXAMPLE 38

4'-Nitro-2,3,3,3-tetrafluoro-2-(trifluoromethyl)propionanilide, m.p., 112-115° C., yield 60% (85% branched isomer).

Analysis calculated for C₁₀ H₅ F₇ N₂ O₃ :

Theory: C, 35.95; H, 1.51; N, 8.38;

Found: C, 36.21; H, 1.50; N, 8.39.

EXAMPLE 39

2'-Chloro-5'-(fluorosulfonyl)-2,3,3,3-tetrafluoro-2-(trifluoromethyl)propionanilide, m.p., 63°-65° C., yield 33% (87% branched isomer).

Analysis calculated for C₁₀ H₄ ClF₈ NO₃ S:

Theory: C, 29.61; H, 0.99; N, 3.45;

Found: C, 29.88; H, 0.98; N, 3.27.

EXAMPLE 40

N-(4-Nitro-1-naphthyl)-2,3,3,3-tetrafluoro-2-(trifluoromethyl)propionamide, m.p., 127-128° C., yield 5% (80% branched isomer).

Analysis calculated for C₁₄ H₇ F₇ N₂ O₃ :

Theory: C, 43.77; H, 1.84; N, 7.29;

Found: C, 43.96; H, 1.82; N, 7.52.

EXAMPLE 41

2'-Bromo-4'-chloro-6'-cyano-2,3,3,3-tetrafluoro-2-(trifluoromethyl)propionanilide, an oil, yield 45% (53% branched isomer).

Analysis calculated for C₁₁ H₃ BrClf₇ N₂ O:

Theory: C, 30.91; H, 0.71; N, 6.55;

Found C, 31.15; H, 0.99; N, 6.30.

EXAMPLE 42

3'-Chloro-4'-nitro-2,3,3,3-tetrafluoro-2-(trifluoromethyl)propionanilide, m.p., 55-57° C., yield 9% (73% branched isomer).

Analysis calculated for C₁₀ H₄ ClF₇ N₂ O₃ :

Theory: C, 32.59; H, 1.09; N, 7.60;

Found: C, 32.55; H, 1.34; N, 7.30.

EXAMPLE 43

2'-Bromo-4'-nitro-2,3,3,3-tetrafluoro-2-(trifluoromethyl)propionanilide was reacted with methyl iodide, in acetone and in the presence of potassium carbonate, yielding N-methyl-2'-bromo-4'-nitro-2,3,3,3-tetrafluoro-2-(trifluoromethyl)propionanilide, an oil, yield 70% (>99% branched isomer).

Analysis calculated for C₁₁ H₆ BrF₇ N₂ O₃ :

Theory: C, 30.94; H, 1.42; N, 6.56;

Found: C, 31.01; H, 1.28; N, 6.77.

EXAMPLE 44

2'-Bromo-4'-nitro-6'-cyano-2,3,3,3-tetrafluoro-2-(trifluoromethyl)propionanilide, m.p., 109°-111° C., yield 10% (30% branched isomer).

Analysis calculated for C₁₁ H₃ BrF₇ N₃ O₃ :

Theory: C, 30.16; H, 0.69; N, 9.59;

Found: C, 30.41; H, 0.62; N, 9.81.

EXAMPLE 45

2'-Methyl-3'-nitro-2,3,3,3-tetrafluoro-2-(trifluoromethyl)propionanilide, m.p., 100°-102° C., yield 55% (82% branched isomer).

Analysis calculated for C₁₁ H₇ F₇ N₂ O₃ :

Theory: C, 37.95; H, 2.03; N, 8.05;

Found: C, 37.68; H, 2.01; N, 8.01.

EXAMPLE 46

2',4'-Dinitro-5'-ethoxy-2,3,3,3-tetrafluoro-2-(trifluoromethyl)propionanilide, m.p., 117°-119° C., was obtained in 10% yield from the attempted purification of crude 2',4'-dinitro-5'-fluoro-2,3,3,3-tetrafluoro-2-(trifluoromethyl)propionanilide with K₂ CO₃ in ethanol (>99% branched isomer).

Analysis calculated for C₁₂ H₈ F₇ N₃ O₆ :

Theory: C, 34.04; H, 1.89; N, 9.93;

Found: C, 34.19; H, 1.80; N, 10.15.

EXAMPLE 47

2'-Bromo-4'-nitro-2,3,3,3-tetrafluoro-2-(pentafluoroethoxy)propionanilide, yield 51%, in mixture with 2'-bromo-4'-nitro-2,2,3,3-tetrafluoro-3-(pentafluoroethoxy)propionanilide and an unidentified third

Analysis calculated for C₁₁ H₄ BrF₉ N₂ O₄ :

Theory: C, 27.56; H, 0.84; N, 5.85;

Found: C, 27.46; H, 0.91; N, 5.75.

EXAMPLE 48

The mixture from the preceding example was purified by treatment with K₂ CO₃ /ethanol, yielding 2-bromo-4'-nitro-2,3,3,3-tetrafluoro-2-(pentafluoroethoxy)propionanilide, m.p., 49° C., yield 50% (14% unidentified third component).

Analysis calculated for C₁₁ H₄ BrF₉ N₂ O₄ :

Theory: C, 27.58; H, 0.84; N, 5.85;

Found: C, 27.80; H, 1.04; N, 6.08.

EXAMPLE 49

2'-Bromo-4'-nitro-2,3,3,3-tetrafluoro-2-(octafluoromorpholino)propionanilide, m.p., 50°-52° C., yield 74% (>99% branched isomer).

Analysis calculated for C₁₃ H₄ BrF₁₂ N₃ O₄ :

Theory: C, 27.20; H, 0.70; N, 7.32;

Found: C, 27.42; H, 0.75; N, 7.32.

EXAMPLE 50

2'-Bromo-4'-nitro-2,3,3,3-tetrafluoro-2-(heptafluoro-n-propoxy)propionanilide, m.p., 49°-51° C., yield 35%. A minor component of 2'-bromo-4'-nitro-2,3,3,3- tetrafluoro-2-(nonafluoro-n-butoxy)propionanilide was detected by F¹⁹ -NMR.

Analysis calculated for C₁₂ H₄ BrF₁₁ N₂ O₄ :

Theory: C, 27.22; H, 0.76; N, 5.29;

Found: C, 26.99; H, 0.72; N, 5.55.

EXAMPLE 51

2',4'-Dinitro-2,3,3,3-tetrafluoro-2-(heptafluoro-n-propoxy)propionanilide, an oil, yield 50%. A minor component of 2',4'-dinitro-2,3,3,3-tetrafluoro-2-(nonafluoro-n-butoxy)propionanilide was detected by F¹⁹ -NMR.

Analysis calculated for C₁₂ H₄ F₁₁ N₃ O₆ :

Theory: C, 29.11; H, 0.81; N, 8.49;

Found: C, 29.31; H, 1.05; N, 8.56.

EXAMPLE 52

2'-Bromo-4'-nitro-2-(trifluoromethyl)-2,3,3,4,4,5,5,5-octafluorovaleranilide, m.p., 39°-40° C., yield 44% (isomer pure).

Analysis calculated for C₁₂ H₄ BrF₁₁ N₂ O₃ :

Theory: C, 28.07; H, 0.78; N, 5.46;

Found: C, 28.42; H, 0.96; N, 5.67.

EXAMPLE 53

2'-(Trifluoromethyl)-4'-bromo-2,3,3,3-tetrafluoro-2-(trifluoromethyl)propionanilide, m.p., 37°-40° C., yield 49% (81% branched isomer).

Analysis calculated for C₁₁ H₄ BrF₁₀ NO:

Theory: C, 30.30; H, 0.92; N, 3.21;

Found: C, 30.07; H, 1.02; N, 3.20.

EXAMPLE 54

2',5'-Dichloro-4'-nitro-2,3,3,3-tetrafluoro-2-(trifluoromethyl)propionanilide, octadecyltrimethylammonium salt monohydrate, m.p., 80°-82° C., yield 99% (96% branched isomer).

Analysis calculated for C₃₁ H₅₀ Cl₂ F₇ N₃ O₄ :

Theory: C, 51.81; H, 7.01; N, 5.74;

Found: C, 49.75; H, 5.56; N, 5.42.

EXAMPLE 55

2',5'-Dichloro-4'-nitro-2,3,3,3-tetrafluoro-2-(trifluoromethyl)propionanilide, hexadecyltrimethylammonium salt, monohydrate, m.p., 79°-81° C., yield 99% (94% branched isomer).

Analysis calculated for C₂₉ H₄₆ Cl₂ F₇ N₃ O₄ :

Theory: C, 49.43; H, 6.53; N, 5.96;

Found: C, 47.65; H, 6.11; N, 7.16.

EXAMPLE 56

2'-Cyano-4'-nitro-2,3,3,3-tetrafluoro-2-(heptafluoro-n-propoxy)propionanilide, m.p. 96° C., yield 17%. A minor component of 2'-cyano-4'-nitro-2,3,3,3-tetrafluoro-2-(nonafluoro-n-butoxy)propionanilide was detected by F¹⁹ -NMR

Analysis calculated for C₁₃ H₄ F₁₁ N₃ O₄ :

Theory: C, 32.86; H, 0.85; N, 8.84;

Found: C, 33.06; H, 1.14; N, 8.69.

EXAMPLE 57

2',4'-Dinitro-5'-fluoro-2,3,3,3-tetrafluoro-2-(heptafluoro-n-propoxy)propionanilide, an oil, yield 62%. A minor component of 2',4'-dinitro-5'-fluoro-2,3,3,3-tetrafluoro-2-(nonafluoro-n-butoxy)propionanilide was detected by F¹⁹ -NMR.

Analysis calculated for C₁₂ H₃ F₁₂ N₃ O₆ :

Theory: C, 28.09; H, 0.59; N, 8.19;

Found: C, 27.99; H, 0.75; N, 8.27.

EXAMPLE 58

2',4'-Dinitro-2-(trifluoromethyl)-2,3,3,4,4,-5,5,5-octafluorovaleranilide, an oil, yield 13%.

Analysis calculated for C₁₂ H₄ F₁₁ N₃ O₅

Theory: C, 36.08; H, 0.84; N, 8.77;

Found: C, 30.36; H, 0.88; N, 8.98.

EXAMPLE 59

2',4'-Dinitro-5'-fluoro-2-(trifluoromethyl)-2,3,3,4,4,5,5,5-octafluorovaleranilide, an oil, yield 58%.

Analysis calculated for C₁₂ H₃ F₁₂ N₃ O₅ :

Theory: C, 28.99; H, 0.61; N, 8.45;

Found: C, 29.20; H, 0.84; N, 8.71.

EXAMPLE 60

2'-Bromo-4'-chloro-6'-cyano-2,3,3,3-tetrafluoro-2-(heptafluoro-n-propoxy)propionanilide, an oil, yield 51%. A minor component of 2'-bromo-4'-chloro-6'-cyano-2,3,3,3-tetrafluoro-2-(nonafluoro-n-butoxy)propionanilide was detected by F¹⁹ -NMR.

Analysis calculated for C₁₃ H₃ BrClF₁₁ N₂ O₂ :

Theory: C, 29.21; H, 0.61; N, 5.68;

Found: C, 29.41; H, 0.87; N, 5.48.

EXAMPLE 61 2'-Bromo-4'-nitro-2,3,3,4,4,5,5,6,6,6-decafluoro-2-(pentafluoroethyl)hexananilide.

This compound was prepared from 2,3,3,4,4,5,-5,6,6,6-decafluoro-2-(pentafluoroethyl)hexanoic acid by conversion to the acid fluoride by electrochemical fluorination as follows:

In a Teflon jar equipped with a stainless steel condensor maintained at from -40° to -50° C., approximately 80 cc of commercial anhydrous HF underwent a pre-electrolysis to remove the last traces of water. An electrode pack of about 2 in³ in size consisting of alternating nickel and carbon steel plates was used under a nitrogen atmosphere at a maximum current density of about 20 ma/cm² and at or below a cell voltage of 5.2 volts relative to a copper reference electrode. 4.1 g of the acid was added and approximately 0.5 amp hrs was passed. The reaction mixture was extracted with four 20 cc portions of CFCl₃, and the extracts were added to 1.6 g of 2-bromo-4-nitroaniline and 1.5 g of triethylamine in 25 cc of methylene chloride. The organic layer was washed with dilute HCl, dried over magnesium sulfate, evaporated, and the residue was chromatographed on silica gel with toluene to give a crude mixture whose F¹⁹ -NMR spectrum was consistent with the desired product. The crude mixture was chromatographed again with ethylacetate/hexane (1:5) to produce 100 mg of the desired anilide, an oil, in 1.6% yield.

Analysis calculated for C₁₄ H₄ BrF₁₅ N₂ O₃ :

Theory: C, 27.43; H, 0.66; N, 4.57;

Found: C, 27.56; H, 0.73; N, 4.75.

Representative other examples of the present invention include the following compounds:

2'-bromo-4'-nitro-2-chloro-3,3,3-trifluoro-2-(trifluoromethyl)propionanilide

2'-bromo-4'-nitro-2-bromo-3,3,3-trifluoro-2-(trifluoromethyl)propionanilide

2'-bromo-4'-nitro-3,3,3-trifluoro-2,2-bis(trifluoromethyl)propionanilide

2'-bromo-4'-nitro-2,3,3,4,4,4-hexafluoro-2-(trifluoromethyl)butyranilide

2'-bromo-4'-nitro-2,3,3,3-tetrafluoro-2-(trifluoromethoxy)propionanilide

2'-bromo-4'-nitro-2-cyano-2,3,3,3-tetrafluoropropionanilide

2'-bromo-4'-nitro-2,3,3,3-tetrafluoro-2(bis(pentafluoroethyl)amino)propionanilide

2'-bromo-4'-nitro-2,2-bis(trifluoromethyl)propionanilide

2'-bromo-4'-nitro-2,3,3,3-tetrafluoro-2-(trifluoromethyl)propionanilide, sodium salt

2'-bromo-4'-nitro-2,3,3,3-tetrafluoro-2-(trifluoromethyl)propionanilide, tris(2-hydroxyethyl)ammonium salt

2'-bromo-4'-nitro-2-chloro-3,3,3-trifluoro-2-(trifluoromethyl)propionanilide, tris(2-hydroxypropyl)ammonium salt

2'-bromo-4'-nitro-3,3,3-trifluoro-2,2-bis(trifluoromethyl)propionanilide, tetra(3-hydroxypropyl)ammonium salt

2,3,3,3-tetrafluoro-2-(trifluoromethyl)-N-(2-bromo-4-nitro-1-naphthyl)propionamide

2,3,3,3-tetrafluoro-2-(trifluoromethyl)-N-(2-bromo-4-nitro-1-naphthyl)propionamide, tetra-n-propylammonium salt

Insecticidal Utility

As noted above, the compounds of the present invention exhibit excellent insecticidal and arachnicidal activity. This activity is illustrated by the following tests.

Mite-Insect Screen

Various representative compounds were evaluated in the mite-insect screen. This screen was conducted with four insect and mite species; the compound of EXAMPLE 1 was additionally evaluated in a separate test against three species. Each compound was formulated in the following procedure: the compound sample was dissolved in a suitable solvent, typically a 50/50 mixture of reagent grade acetone and 95% ethyl alcohol containing Toximul R and Toximul S (each of these is a sulfonate-nonionic blend of emulsifiers produced by Stepan Chemical Co.), and the solution was thereafter diluted with deionized water to the desired concentration. Specific test methods for various species in the mite-insect screen are set forth below.

Southern Armyworm

Young squash plants (Cucurbita maxima, var. Blue Hubbard) were sprayed with a formulation containing the test compound; the spraying was of both the tops and bottoms of the leaves, about 8-10 ml per plant. The plants were then allowed to dry and the leaves removed.

The leaves were placed in 100×20 mm plastic petri dishes containing third-instar larvae of southern armyworm (Spodoptera eridania (Cramer), Order Lepidoptera, Family Noctuidae). Two replicates were carried out.

Mortality counts were made four days after the larvae were placed on the treated leaves. Observations were also made to determine any inhibition of feeding.

Twospotted Spider Mite & Melon Aphid

Young squash plants (Cucurbita maxima, var. Blue Hubbard) were infested by placing on each cotyledon a bean leaf infested with twospotted spider mite (Tetranychus urticae (Koch), Order Acarina, Family Tetranychidae). The plants were held for a day, then sprayed to wetting with a formulation containing the test compound, with one infested cotyledon per treatment. Mortality was determined one day after treatment.

Another cotyledon was similarly infested with approximately 100 nymphs and adults of melon aphid (Aphis gossypii Glover, Order Homoptera, Family Aphididae). Mortality was determined one day after spraying.

Corn Rootworm

A presoaked corn seed, 15 grams of dry sandy soil, and 2 ml of tap water were mixed in a one-ounce plastic container. The mixture was then treated with 1 ml of a formulation containing the test compound and subsequently permitted to dry for 6-12 hours. The concentration of each test compound in the soil was 12 ppm. Five larvae of southern corn rootworm (Diabrotica undecimpunctata howardi Barber, Order Coleoptera, Family Chrysomelidae) were added to each container, which was then capped and held at 23° C. Mortality to southern corn rootworm and phytotoxicity to the corn seedling were recorded at four days posttreatment.

The compound of Example 1 was tested in the mite-insect screen against only three organisms, southern armyworm, twospotted spider mite, and melon aphid, at test concentrations of 100 ppm and 50 ppm. Employing a scale of 0=no control, to 3=complete control, the compound was rated 0 on southern armyworm at both concentrations, 3 on twospotted spider mite at both test concentrations, and 3 on melon aphid at both concentrations.

Other compounds of the present invention were tested against all four organisms with a formulation containing 200 ppm of the test compound; in the case of corn rootworm test, the resulting concentration of the test compound in the soil was 12 ppm. Results were recorded as percent control. Any inhibition of feed intake was noted as an "X". The results of these tests are recorded in the following table.

                                      TABLE I                                      __________________________________________________________________________     MITE-INSECT SCREEN                                                             EX.                                                                               CORN ROOTWORM                                                                             SO. ARMYWORM                                                                               2SSMITE   MEL0N APHID                                NO.                                                                               PERCENT MORT.                                                                             % CONT.                                                                              FEED.IN.                                                                             PERCENT CONT.                                                                            PERCENT CONT.                              __________________________________________________________________________      1 100        0           100       100                                         4  60        0           100       100                                         5 100        0           100       20                                          6 100        0           100       100                                         7 100        0           0         0                                           8 100        0           100       70                                          9 100        0           0         0                                          10 100        0           0         80                                         11 100        0           40        0                                          12 100        100   X     90        90                                         13 100        0           100       100                                        14  0         0           40        40                                         15 100        0           20        0                                          16 100        0           100       100                                        17 100        80    X     100       90                                         18 100        0           40        0                                          19 100        100   X     60        0                                          20  20        0           20        30                                         21 100        0           100       100                                        22 100        0           100       100                                        23  60        0           70        30                                         24 100        0           100       90                                         25 100        0           100       100                                        26 100        0           100       100                                        27 100        0           90        90                                         27 100        0           100       100                                        28 100        0           90        90                                         29 100        0           100       100                                        30 100        0           100       100                                        31 100        0           100       100                                        31 100        0           0         0                                          32 100        0           100       100                                        33 100        60          100       100                                        34 100        0           100       50                                         35 100        0           0         20                                         36 100        0           100       90                                         37 100        0           90        90                                         38  0         0           0         0                                          39  40        0           0         0                                          40  40        100   X     100       50                                         41  0         0           80        0                                          41 100        0           80        0                                          42  0         0           0         0                                          43  0         0           40        10                                         44  0         0           100       50                                         44  0         0           0         0                                          45  0         0           0         0                                          47 100        0           80        80                                         48 100        0           50        50                                         49 100        0           0         0                                          50 100        0           100       100                                        51 100        0           100       100                                        51  60        0           100       100                                        52 100        0           100       100                                        53 100        0           0         0                                          54 100        0           100       100                                        55 100        100         100       100                                        56 100        0           0         0                                          __________________________________________________________________________

Twospotted Spider Mite

Selected compounds of the present invention were evaluated against twospotted spider mite in a secondary test. For this test, each compound was formulated using the solvent/emulsifier described above for the mite-insect screen. The test procedure was essentially the same as that described above as part of the mite-insect screen.

                  TABLE II                                                         ______________________________________                                         Twospotted Spider Mite                                                         Example                                                                        No.    500     100    50    10   5     2.5 1.0  ppm                            ______________________________________                                          1     100      89          48                                                  4     100     100                                                              4     100     100          100                                                 5     100     100                                                              5     100     100          75                                                  5     100     100           9                                                  6     100     100                                                              6     100     100          91                                                  6     100      90           1                                                  8     100      92          96                                                  8      30      17           2                                                 11     100     100          83                                                 13     100     100          83                                                 16     100     100          40                                                 17     100     100          100                                                19     100                                                                     19     100            63     3                                                 21     100     100          100                                                22     100     100          71                                                 24     100     100          94                                                 24     100     100          53                                                 24                          95   32        0                                   24                          23   10        0                                   25     100     100                                                             25     100      99                                                             25             100          72   76        0                                   25              88          12   3         0                                   26     100     100          92                                                 26     100      64          65                                                 26                          85   18        0                                   26                          66   5         2                                   27     100     100                                                             27     100                                                                     27     100                                                                     27             100          27   13        3                                   27              86           8   5         2                                   28     100     100                                                             28      96     100                                                             28             100          76   2         0                                   28             100          59   9         0                                   29     100     100                                                             29             100          39             6                                   30     100      96                                                             30              99    85    12             1                                   31     100     100          51                                                 32     100     100                                                             32             100    100   56             0                                   33     100      96          49                                                 34      99     100          91                                                 34     100      98          13                                                 34     100     100                                                             36     100     100          100                                                36     100      63          13                                                 37     100     92           63                                                 52     100     15      0*    0   0         0                                   ______________________________________                                          *25 ppm, also 0.                                                         

Twospotted Spider Mite Pre and Post Application

Two compounds of the present invention were tested further against twospotted spider mite on squash. The formulation and test procedures were as described above except that in some treatments, the formulation containing the test compound was applied to the foliage prior to introduction of the mites ("pre") whereas in other treatments, the formulation containing the test compound was applied to the foliage after the introduction of the mites ("post"). Results were as set forth in the following table.

                  TABLE III                                                        ______________________________________                                         Twospotted Spider Mite                                                         Pre and Post Application                                                       Example                                                                               Treatment                                                               No.    Rate (ppm)  Applied Before                                                                             Applied After                                   ______________________________________                                         34     10          94          31                                                     5           45          9                                                      2.5         8           4                                                      1.0         3           3                                               36     10          100         13                                                     5           70          17                                                     2.5         14          14                                                     1.0         6           0                                               ______________________________________                                    

Cotton Bollworm

In another secondary test, selected compounds of the present invention were evaluated against cotton bollworm (Heliothis zea Boddie). Each compound undergoing test was formulated using the solvent/emulsifier described above in the mite-insect screen.

Twenty first-instar cotton bollworms were placed in a petri dish containing filter paper, then treated with 2 ml of test compound solution. Bollworms were allowed to remain in the dish for 1 hour, then transferred to media cups.

Twenty-four hours after treatment, the bollworms were observed and the percent mortality determined. Compounds active in an initial test were tested at lower concentrations, by the same procedure. Results were as set forth in the following table.

                  TABLE IV                                                         ______________________________________                                         Cotton Bollworm                                                                Example                                                                        No.         500    100        10   ppm                                         ______________________________________                                         12           18     8                                                          17          100    100                                                         19          100    80                                                          24          100    100        0                                                24          100    87         63                                               25           90                                                                25          100    100        0                                                26          100                                                                26          100    90         0                                                27           90                                                                28          100                                                                28           70    40         0                                                33          100    100                                                         ______________________________________                                    

Corn Leafhopper-Contact

In yet another secondary test, selected compounds were evaluated for their ability to control leafhopper (Dalbulus maidis Delong and Wolcott Order Homoptera, Family Cicadellidae) on corn (Zea mays Linne). Each compound was dissolved in acetone to produce varying concentration solutions of the compound.

A total of two ml of each solution was then applied to a filter paper in a petri dish lid. After the compound saturated the filter paper, a dental wick moistened with deionized water and a kernel of corn were placed on the filter paper. Ten leafhoppers which had been anesthetized with CO₂ were then placed in the dish. Each treated filter paper was covered with a petri dish bottom, ventilated by a 1 cm hole covered with fine mesh screen.

Observations were made 24 hours later to determine percent mortality. Compounds exhibiting activity in the initial test were tested in the same procedures but at lower concentrations. Results were as set forth in the following table.

                                      TABLE V                                      __________________________________________________________________________     Corn Leafhopper-Contact                                                        Example                                                                        No.  500                                                                               200                                                                               100                                                                               50 25 12.5                                                                              10 6.25                                                                              3.125                                                                             1 ppm                                          __________________________________________________________________________      1      100                                                                               100         90                                                       4      100                                                                     4          10          0                                                       8         100                                                                  8         100                                                                               100      60                                                      10      100                                                                    13      100                                                                               100         70                                                      16   100    80          0                                                      17    80    80         40                                                      21   100   100         80                                                      22   100   100         90                                                      24         100                                                                               100      70                                                      25         100                                                                               100      80       30                                             25            100                                                                               100                                                                               100   60 60                                                26         100                                                                               100      70       50                                             26            100                                                                               100                                                                               80    70 40                                                27         100                                                                               100      50       30                                             27            100                                                                                80                                                                               70    60 70                                                28          50                                                                                70      40        0                                             29         100         44        0                                             30         100                                                                 30          90                                                                                90      60                                                      31         100                                                                 31         100                                                                               100      80                                                      32         100                                                                 32         100                                                                               100      80                                                      33   100   100         20                                                      36         100                                                                 36         100                                                                                70      40                                                      37      100                                                                               100         90                                                      __________________________________________________________________________

Corn Leafhopper--on Corn

Three compounds of the present invention were evaluated for the control of corn leafhopper on corn. Each compound was formulated essentially as described above for the mite-insect screen. The testing procedure was the same as described for the twospotted spider mite except that the host plant was corn. The concentration of each compound in its treating formulation was 200 ppm. The results were as set forth in the following table.

                  TABLE VI                                                         ______________________________________                                         Corn Leafhopper - on Corn                                                      Example No.   Percent Control                                                  ______________________________________                                         4             100                                                              6             80                                                               10            50                                                               ______________________________________                                    

Southern Corn Rootworm

In a secondary test, selected compounds were reevaluated against southern corn rootworm. The test method was the same as described above as part of the mite-insect screen, with the exception that the compounds were tested at differing concentrations, that two replicates per treatment were carried out, and that mortality ratings were made at differing numbers of days after treatment. The results were as set forth in the following table.

                  TABLE VII                                                        ______________________________________                                         Corn Rootworm                                                                         PPM of       Percent      Days                                          Example                                                                               Compound     Control of   Post-                                         No.    in soil      Corn Rootworm                                                                               Treatment                                     ______________________________________                                          1     3.0          100          2                                                    1.5          100          2                                                    0.75         100          2                                                    0.38         100          2                                                    0.19         30           2                                                    0.09         40           2                                                    3.0          100          4                                                    1.5          100          4                                                    0.75         100          4                                                    0.38         100          4                                                    0.19         90           4                                                    0.09         60           4                                                    0.75*        100          1                                                    0.38*        100          1                                                    0.19*        85           1                                                    0.09*        0            1                                                    0.75*        100          3                                                    0.38*        100          3                                                    0.19*        90           3                                                    0.09*        35           3                                              5     0.75         30           3                                                    0.38         0            3                                                    0.19         0            3                                                    0.09         0            3                                              6     0.75         100          3                                                    0.38         70           3                                                    0.19         50           3                                                    0.09         30           3                                              7     0.75         50           3                                                    0.38         20           3                                                    0.19         0            3                                                    0.09         0            3                                              8     12.0         100          4                                                    6.0          100          4                                                    3.0          100          4                                                    1.5          100          4                                                    0.75         100          4                                                    0.38         100          4                                                    0.19         40           4                                                    0.09         0            4                                                    0.75         100          3                                                    0.38         100          3                                                    0.19         50           3                                                    0.09         10           3                                              9     0.75         0            3                                                    0.38         0            3                                                    0.19         0            3                                                    0.09         0            3                                             10     0.75         0            3                                                    0.38         0            3                                                    0.19         0            3                                                    0.09         0            3                                             11     0.75         50           3                                                    0.38         10           3                                                    0.19         0            3                                                    0.09         0            3                                             12     6.0          100          3                                                    3.0          100          3                                                    1.5          100          3                                                    0.75         60           3                                                    0.38         10           3                                                    0.19         0            3                                                    3.0          100          3                                                    1.5          100          3                                                    0.75         100          3                                                    0.38         70           3                                                    0.19         60           3                                             13     12.0         100          4                                                    6.0          100          4                                                    3.0          100          4                                                    1.5          100          4                                                    0.75         100          4                                                    0.38         80           4                                             14     48.0         80           3                                                    24.0         50           3                                                    12.0         10           3                                             15     6.0          30           3                                                    3.0          0            3                                                    1.5          0            3                                                    0.75         0            3                                                    0.38         0            3                                                    0.19         0            3                                                    6.0          100          4                                                    3.0          100          4                                                    1.5          40           4                                                    0.75         0            4                                                    0.38         0            4                                             16     6.0          100          3                                                    3.0          100          3                                                    1.5          60           3                                                    0.75         0            3                                                    0.38         0            3                                                    6.0          20           3                                                    3.0          0            3                                                    1.5          0            3                                                    0.75         0            3                                                    0.38         0            3                                                    0.19         0            3                                             17     6.0          100          3                                                    3.0          100          3                                                    1.5          100          3                                                    0.75         60           3                                                    0.38         0            3                                             18     6.0          20           3                                                    3.0          0            3                                                    1.5          0            3                                                    0.75         0            3                                                    0.38         0            3                                                    0.19         0            3                                                    6.0          80           4                                                    3.0          0            4                                                    1.5          0            4                                                    0.75         0            4                                                    0.38         0            4                                             19     6.0          60           3                                                    3.0          0            3                                                    1.5          0            3                                                    0.75         0            3                                                    0.38         0            3                                                    6.0          30           4                                                    3.0          10           4                                                    1.5          0            4                                                    0.75         0            4                                                    0.38         0            4                                                    0.19         0            4                                                    0.09         0            4                                             21     6.0          90           3                                                    3.0          30           3                                                    1.5          0            3                                                    0.75         0            3                                                    0.38         0            3                                             22     6.0          40           3                                                    3.0          0            3                                                    1.5          0            3                                                    0.75         0            3                                                    0.38         0            3                                             24     0.75*        100          1                                                    0.38*        100          1                                                    0.19*        90           1                                                    0.09*        35           1                                                    0.75*        100          3                                                    0.19*        100          3                                                    0.09*        50           3                                             25     3.0          100          2                                                    1.5          100          2                                                    0.75         100          2                                                    0.38         100          2                                                    0.75         100          2                                                    0.38         100          2                                                    0.19         70           2                                                    0.09         30           2                                                    0.75         100          3                                                    0.38         80           3                                                    0.09         40           3                                             26     3.0          100          2                                                    1.5          100          2                                                    0.75         100          2                                                    0.38         100          2                                                    0.75         80           2                                                    0.38         30           2                                                    0.19         10           2                                                    0.09         0            2                                                    0.75         100          3                                                    0.38         60           3                                                    0.19         30           3                                                    0.09         0            3                                                    1.5          100          3                                                    0.75         100          3                                                    0.38         40           3                                                    0.19         40           3                                                    0.09         0            3                                             27     6.0          100          3                                                    3.0          100          3                                                    1.5          100          3                                                    0.75         100          3                                                    0.38         40           3                                                    0.19         0            3                                             28     3.0          100          2                                                    1.5          100          2                                                    0.75         100          2                                                    0.38         100          2                                                    1.5          100          3                                                    0.75         100          3                                                    0.38         60           3                                                    0.19         20           3                                                    0.09         10           2                                                    0.75         100          2                                                    0.38         100          2                                                    0.19         50           2                                                    0.09         0            2                                                    0.75         100          3                                                    0.38         100          3                                                    0.19         60           3                                                    0.09         10           3                                             29     6.0          100          3                                                    3.0          100          3                                                    1.5          100          3                                                    0.75         80           3                                                    0.38         40           3                                                    0.19         20           3                                             30     6.0          100          3                                                    3.0          100          3                                                    1.5          100          3                                                    0.75         100          3                                                    0.38         60           3                                                    0.19         0            3                                             31     6.0          100          4                                                    3.0          100          4                                                    1.5          100          4                                                    0.75         100          4                                                    0.38         100          4                                                    0.19         20           4                                                    0.09         0            4                                                    6.0          100          3                                                    3.0          100          3                                                    1.5          100          3                                                    0.75         100          3                                                    0.38         80           3                                                    0.19         40           3                                             32     6.0          100          3                                                    3.0          100          3                                                    1.5          100          3                                                    0.75         100          3                                                    0.38         40           3                                                    0.19         0            3                                             33     6.0          100          4                                                    3.0          100          4                                                    1.5          100          4                                                    0.75         100          4                                                    0.38         100          4                                                    0.19         60           4                                                    0.09         0            4                                             33     3.0          100          3                                                    1.5          100          3                                                    0.75         80           3                                                    0.38         40           3                                                    0.19         0            3                                                    0.09         0            3                                             34     0.75         50           3                                                    0.38         30           3                                                    0.19         10           3                                                    0.09         0            3                                             35     6.0          100          4                                                    3.0          100          4                                                    1.5          100          4                                                    0.75         100          4                                                    0.38         80           4                                                    0.19         40           4                                                    0.09         0            4                                             36     5.0          100          4                                                    5.0          100          4                                                    5.0          100          4                                                    5.0          100          4                                                    5.0          100          4                                                    5.0          100          4                                                    5.0          100          4                                                    5.0          100          4                                                    5.0          100          4                                                    0.75         100          3                                                    0.38         70           3                                                    0.19         10           3                                                    0.09         0            3                                             37     6.0          100          3                                                    3.0          100          3                                                    1.5          100          3                                                    0.75         100          3                                                    0.38         100          3                                                    0.19         50           3                                             40     12.0         90           3                                                    6.0          80           3                                                    3.0          40           3                                             41     12.0         100          3                                                    12.0         100          3                                                    6.0          90           3                                                    6.0          50           3                                                    6.0          30           3                                                    3.0          40           3                                                    3.0          0            3                                                    1.5          0            3                                                    1.5          0            3                                                    0.75         0            3                                                    0.75         0            3                                                    0.38         0            3                                                    0.19         0            3                                             48     12.0         100          4                                                    6.0          100          4                                                    3.0          100          4                                                    3.0          100          1                                                    3.0          100          2                                                    1.5          100          4                                                    1.5          100          1                                                    1.5          100          2                                                    0.75         100          4                                                    0.75         100          1                                                    0.75         100          2                                             48     0.38         40           1                                                    0.38         60           2                                                    0.19         0            1                                                    0.19         0            2                                                    0.09         0            1                                                    0.09         0            2                                             49     12.0         100          4                                                    6.0          100          4                                                    3.0          100          4                                                    3.0          100          1                                                    3.0          100          2                                                    1.5          100          4                                                    1.5          100          1                                                    1.5          100          2                                                    0.75         100          4                                                    0.75         100          1                                                    0.75         100          2                                                    0.38         100          1                                                    0.38         100          2                                                    0.19         30           1                                                    0.19         40           2                                                    0.09         0            1                                                    0.09         0            2                                             50     12.0         100          2                                                    6.0          100          2                                                    6.0          100          3                                                    3.0          100          2                                                    3.0          100          3                                                    1.5          100          2                                                    1.5          100          3                                                    0.75         90           3                                                    0.38         50           3                                             51     12.0         100          2                                                    6.0          50           2                                                    3.0          0            2                                                    1.5          0            2                                                    0.75         0            2                                                    0.38         0            2                                                    0.19         0            2                                                    0.09         0            2                                                    0.04         0            2                                             52     12.0         100          5                                                    6.0          100          5                                                    3.0          100          5                                                    3.0          100          5                                                    1.5          100          5                                                    1.5          100          5                                                    0.75         90           5                                                    0.38         70           5                                                    0.19         40           5                                                    0.09         10           5                                                    0.04         0            5                                             56     12.0         100          4                                                    6.0          100          4                                                    3.0          90           4                                                    1.5          50           4                                                    0.75         0            4                                                    0.38         0            4                                                    0.19         0            4                                                    0.09         0            4                                                    0.04         0            4                                             ______________________________________                                          *four replicates                                                         

Southern Corn Rootworm-Residual Test

Selected compounds were evaluated for residual control of southern corn rootworm. The test was conducted as follows. Each compound was dissolved in acetone, sprayed onto soil, and mixed well. The soil was added, in a 1" deep layer, to pots already containing 3" of untreated soil with 3 corn seeds on top. The pots were held under normal greenhouse conditions for 21 days, at which time average crown root length measurements were made, on a minimum of 9 plants per treatment. Additionally, all soil was removed from each pot, mixed well, and bioassayed with 3rd instar southern corn rootworm larvae (Diabrotica undecimpunctata howardi Barber, Order Coleoptera, Family Chrysomelidae). There were three replicates per treatment.

Phytotoxicity was evaluated in either of two methods. In a first method, used for most of the tests, the average crown root length was determined; crown root length in the controls varied from about 110 to about 150 mm and averaged about 120 mm. In the second method, crown root area was measured by a LI-COR Model LI-3000 portable area meter, with the controls regarded as 100 percent and other treatments reported as a percent of control.

Results were as set forth in the following table.

                  TABLE VIII                                                       ______________________________________                                         Corn Rootworm-Residual                                                                  Avg. Crown    Precent Mortality                                       Treatment,                                                                              Root Length (mm)                                                                             Corn Rootworm                                           Example #                                                                               8      4       2    8     4    2     PPM                              ______________________________________                                          1       20     25      67   100   100  27                                      6        0      0      25   100   100  100                                     8        8     38      75    87   87   27                                     24       53     82      102  100   26   34                                     24       21     33      58   100   100  33                                     24       20     54      81   100   100  40                                     25       16     52      62    40    0    0                                     26       44     54      93   100   87   33                                     28       49     77      90    53   13    0                                     29       34     53      103   87   53    7                                     30       30     42      71    60   80    0                                     31       24     43      83   100   20    0                                     32       33     51      58    80   60    0                                     35       15     36      80   100   100  73                                     36       37     85      97   100   100  87                                     48        5*     17*     26* 100   100  87                                     49        21*    17*     35* 100   100   7                                     50        9*     24*     47* 100   73   27                                     ______________________________________                                          *Percent of crown roots                                                  

Corn Rootworm--Field Test

The compound of Example 24 was evaluated for the control of corn rootworm in the field, at a site known to be naturally infested with Diabrotica spp. The compound was formulated as a 10% granule, as described below in Example A. Field corn was planted and the granular formulation was applied two days later in a seven-inch band along the row. Ratings were made of various parameters:

Crop Emergence, 12 days=scale of 0-10, with 0=no effect on emergence and 10=no emergence

Crop Stand Count, 34 days=% of control

Crop Vigor Rating, 20 days=% of control

Root Injury Rating, 20 days=scale of 0-100, with 0=no injury and 100=maximum injury

Root Injury Rating, 42 days=scale of 0-100, with 0=no injury and 100=maximum injury

Rootworm Damage Rating, 42 days=1-6, with 1=no damage and 6=maximum damage

Results are recorded in the following table.

                                      TABLE IX                                     __________________________________________________________________________     Corn Rootworm - Field Test                                                            Crop  Crop Crop Root Root Rootworm                                             Emergence                                                                            Stand                                                                               Vigor                                                                               Injury                                                                              Injury                                                                              Damage                                               Rating                                                                               Count                                                                               Rating                                                                              Rating                                                                              Rating                                                                              Rating                                        Treatment*                                                                            (12 days)                                                                            (34 days)                                                                           (20 days)                                                                           (20 days)                                                                           (42 days)                                                                           (42 days)                                     __________________________________________________________________________     Compound of                                                                    Example 24                                                                     0.5 lb/acre                                                                           0     97.3 100  0    3    2.1                                           1.0 lb/acre                                                                           0     86.3 100  0    12   1.8                                           Fonofos                                                                        0.5 lb/acre                                                                           0     93.1 100  0    1    2.4                                           1.0 lb/acre                                                                           0     91.8 100  0    0    3.0                                           2.0 lbs/acre                                                                          0     91.8 100  0    0    2.1                                           chlorpyrifos                                                                   0.5 lb/acre                                                                           0     101.4                                                                               100  0    0    2.3                                           1.0 lb/acre                                                                           0     101.4                                                                               100  0    0    2.1                                           2.0 lbs/acre                                                                          0     97.3 100  0    0    2.2                                           terbufos                                                                       0.5 lb/acre                                                                           0     91.8 100  0    0    2.0                                           1.0 lb/acre                                                                           0     102.7                                                                               100  0    0    2.2                                           2.0 lbs/acre                                                                          0     98.6 100  0    0    2.0                                           phorate                                                                        0.5 lb/acre                                                                           0     104.1                                                                               100  0    0    2.3                                           1.0 lb/acre                                                                           0     95.9 100  0    1    2.9                                           2.0 lbs/acre                                                                          0     101.4                                                                               100  0    1.5  2.3                                           carbofuran                                                                     0.5 lb/acre                                                                           0     102.7                                                                               100  0    0    2.0                                           1.0 lb/acre                                                                           0     110.9                                                                               100  0    0    2.0                                           2.0 lbs/acre                                                                          0     90.4 100  0    2.0  1.9                                           trimethacarb                                                                   0.5 lb/acre                                                                           0     97.3 100  0    0    1.9                                           1.0 lb/acre                                                                           0     94.5 100  0    0    2.1                                           2.0 lbs/acre                                                                          0     95.9 100  0    0    2.0                                           isofenphos                                                                     0.5 lb/acre                                                                           0     93.1 100  0    0    2.0                                           1.0 lb/acre                                                                           0     97.3 100  0    0    1.8                                           2.0 lbs/acre 97.3 100  0    0    2.0                                           control                                                                               0     100  100  0    0    2.7                                           __________________________________________________________________________      *0.5 lb/acre = 0.56 kg/ha                                                      1.0 lb/acre = 1.12 kg/ha                                                       2.0 lbs/acre = 2.24 kg/ha                                                

Black Cutworm

The compounds of Examples 1 and 36 were evaluated for the control of black cutworm (Agrotis ipsilon (Hufnagel) Order Lepidoptera, Family Noctuidae). Each compound was dissolved in acetone and the solution was pipetted onto sandy loam soil to obtain the desired soil concentration. The treated soil was transferred onto a petri dish and allowed to air dry for 24 hours. Laboratory reared 3rd-4th-instar black cutworm larvae were then introduced into the treated soil; corn seedlings were supplied as a food source. There were two replicates per treatment. Mortality readings were made three days post treatment. Results were as set forth in the following table.

                  TABLE X                                                          ______________________________________                                         Black Cutworm #1                                                               Treatment      Percent Control                                                 ______________________________________                                         Compound of                                                                    Example 1                                                                      24.0           70                                                              12.0           20                                                              6.0            0                                                               3.0            0                                                               1.5            0                                                               Compound of                                                                    Example 36                                                                     24.0           40                                                              12.0           0                                                               6.0            0                                                               3.0            0                                                               1.5            0                                                               terbufos                                                                       24.0           100                                                             12.0           100                                                             6.0            50                                                              3.0            0                                                               1.5            0                                                               0.75           0                                                               0.38           0                                                               chlorpyrifos                                                                   24.0           100                                                             12.0           100                                                             6.0            100                                                             3.0            100                                                             1.5            10                                                              0.75           0                                                               0.38           0                                                               Control        0                                                               ______________________________________                                          *Scale of                                                                      0 = none                                                                       1 = 1-50%                                                                      2 = 51-99%                                                                     3 = 100%                                                                 

The same compounds were evaluated again for the control of black cutworm, employing the same procedures except that there were four replicates and that mortality readings were made four days post treatment. Results were as set forth in the following table.

                  TABLE XI                                                         ______________________________________                                         Black Cutworm #2                                                               Treatment      Percent Control                                                 ______________________________________                                         Compound of                                                                    Example 1                                                                      48 ppm         100                                                             24 ppm         15                                                              12 ppm         10                                                              Compound of                                                                    Example 36                                                                     48 ppm         65                                                              24 ppm         0                                                               12 ppm         0                                                               chlorpyrifos                                                                   12 ppm         100                                                             6 ppm          100                                                             3 ppm          100                                                             1.5 ppm        100                                                             terbufos                                                                       12 ppm         100                                                             6 ppm          100                                                             3 ppm          100                                                             1.5 ppm        100                                                             control        0                                                               ______________________________________                                    

Diamondback Moth

Selected compounds of the present invention were evaluated for the control of the larval stage of the diamondback moth (Plutella xylostella (Linne) Order Lepidoptira, Family Plutellidae). For each test, a petri dish base and its lid were lined with filter paper, and both were placed in a cabinet and sprayed with a solution of the compound to supply 50 ml of solution per 0.5 square meter of surface area. The papers were allowed to dry for 3 hours at 25° C. Five 3rd-4th-instar larvae were placed in each petri dish base and the lid placed on it. After one hour, and daily thereafter, an untreated Chinese cabbage leaf disc was supplied as food. After two days, the number of live larvae was determined and percent control was calculated. Tests were conducted with both a wild strain ("susceptible") and a strain resistant to carbamate, pyrethroid, organochlorides and organophosphate insecticides ("resistant"). Results were as set forth in the following table.

                  TABLE XII                                                        ______________________________________                                         Diamondback Moth                                                                          Percent Control                                                     Treatment  12.5 ppm 25 ppm    50 ppm                                                                               100 ppm                                    ______________________________________                                         Compound of                                                                    Example 1                                                                      Resistant  100      100       100   100                                        Susceptible                                                                               100      100       100   100                                        Compound of                                                                    Example 36                                                                     Resistant  67        78        89   100                                        Susceptible                                                                               31       100        93   100                                        Cypermethrin                                                                   Resistant  --        11        22    33                                        Susceptible                                                                               --        31       100   100                                        ______________________________________                                    

German Cockroach

The compounds of Examples 24-28 were evaluated for the control of German cockroach (Blattella germanica (Linne) Order Orthoptera, Family Blattellidae). The evaluation was carried out by dissolving the compound in the same solvent/emulsifier mixture employed in the mite-insect test above, and pouring 2 ml of the solution onto a filter paper in a petri dish. Ten German cockroaches were immediately placed in the petri dish and held there for 24 hours at which time the percent mortality was determined. Results were as set forth in the following table.

                  TABLE XIII                                                       ______________________________________                                         German Cockroach                                                               Example                                                                        No.         500    100         10    PPM                                       ______________________________________                                         24          100    40           0                                              25          100                                                                26          60                                                                 27          80                                                                 28          40                                                                 ______________________________________                                    

Summary of Additional Trials

The compounds of Examples 1 and 36 were evaluated for the control of corn rootworm at numerous locations throughout the midwestern U.S. Observations were also made for various parameters of phytotoxicity. Each compound was formulated as a 10% granule; application rates were 0.85-3.4 grams/100 row feet. At most locations, each of the compounds controlled corn rootworm with no phytotoxicity. At some locations, phytotoxicity was observed, especially at higher rates. The phytotoxicity took the form of some delay in emergence, and the compound of Example 1 in addition showed crop injury on emergence, early and midseason root injury, and midseason crop injury. The phytotoxicity was observed despite the fact that many of the trials employed post presswheel placement, therefore suggesting the need for even better separation of the present compounds from the corn seed or a safer formulation.

In European field trials at 1-4 kg/ha on wheat, potatoes, and sugar beets, each of the compounds controlled wireworm.

However, the compound of Example 1 exhibited crop injury to wheat and potatoes, and both compounds exhibited unacceptable crop injury to sugar beets.

Application of Example 36 to bluegrass showed no injury. Although no insecticidal efficacy data were obtained in the trial, the finding suggests that the present compounds can be used for the control of turf insects. Cf. Tables X and XI.

The foregoing illustrates that the compounds of the present invention are effective against a number of insects and arachnids, including organisms that attack foliage as well as organisms that live in the soil and attack roots and other underground parts of plants. Therefore, in another embodiment, the present invention is directed to a method of inactivating an insect or arachnid which comprises applying to a locus of the insect or arachnid an effective amount of one or more of the compounds of the present invention.

Insects and arachnids against which the present method can be practiced include the various species identified above as well as many others, including, among the insects, the following

Coleoptera

Anthonomus grandis--boll weevil

Conotrachelus nenuphar--plum curculio

Curculio caryae--pecan weevil

Diabrotica spp.--rootworm and cucumber beetles

Echinocnemus squameus--rice plant weevil

Epitrix hirtipennis--tobacco flea beetle

Eutheola humilis rugiceps--sugarcane beetle

Hypera postica--alfalfa weevil

Leptinotarsa decimlineata--Colorado potato beetle

Lissorhoptrus oryzophilus--rice water weevil

Oulema oryzae--rice leaf beetle

Phyllotreta striolata--striped flea beetle

Melanotus spp. and Agriotes spp.--wireworms

Stenolophus lecontei--seedcorn beetle

Popillia japonica--Japanese beetle

Sphenophorus maidis--maize billbug

Systena blanda--palestriped flea beetle

Diptera

Contarinia sorghicola--sorghum midge

Dacus dorsalis--oriental fruit fly

Liriomyza spp.--leaf miner

Rhagoletis pomonella--apple maggot

Hylemia spp. and Delia spp.--root and seed maggots

Heteroptera

Anasa tristis--squash bug

Blissus leucopterus leucopterus--chinch bug

Euschistus servus--brown stink bug

Lygus lineolaris--tarnished plant bug

Nezara viridula--southern green stink bug

Oebalus pugnax--rice stink bug

Pseudatomoscelis seriatus--cotton fleahopper

Homoptera

Clastoptera achatina--pecan spittlebug

Empoasca fabae--potato leafhopper

Eriosoma lanigerum--wooly apple aphid

Fiorinia theae--tea scale

Graminella nigrifrons--blackfaced leafhopper

Icerya purchasi--cottony cushion scale

Laodelphax striatellus--small brown planthopper

Lepidosaphes ulmi--oystershell scale

Myzus persicae--green peach aphid

Nephotettix cincticeps--green rice leafhopper

Niloparvata lugens--brown rice planthopper

Phylloxera devastatrix--pecan phylloxera

Planococcus citri--citrus mealybug

Psylla pyricola--pear psylla

Quadraspidiotus perniciosus--San Jose scale

Rhopalosiphum maidis--corn leaf aphid

Sipha flava--yellow sugarcane aphid

Sogatella furcifera--whitebacked planthopper

Spissisti festinus--threecornered alfalfa hopper

Trialeurodes vaporariorum--greenhouse whitefly

Anuraphis maidiradicis--corn root aphid

Hymenoptera

Atta spp.--leafcutter ants

Camponotus spp.--carpenter ants

Dolichovespula spp.--yellowjackets

Solenopsis invicta--red imported fire ant

Tetramorium caespitum--pavement ant

Vespidae spp.--hornets, wasps

Isoptera

Coptotermes formosanus--Formosan subterranean termite

Reticulitermes flavipes--eastern subterranean termite

Lepidoptera

Agrotis spp. and other genera--cutworms

Alabama argillacea--cotton leafworm

Anticarsia gemmatalis--velvetbean caterpillar

Buccalatrix thurberiella--cotton leafperforator

Chilo suppressalis--rice stem borer

Choristoneura fumiferana--spruce budworm

Cydia pomonella--codling moth

Elasmopalpus lignosellus--lesser cornstalk borer

Grapholita molesta--oriental fruitmoth

Heliothis virescens--tobacco budworm

Heliothis zea--cotton bollworm

Keiferia lycopersicella--tomato pinworm

Ostrinia nubilalis--European corn borer

Parnara guttata--rice skipper

Pectinophora gossypiella--pink bollworm

Pieris rapae--imported cabbageworm

Plutella xylostella--diamondback moth

Pseudoplusia includens--soybean looper

Sesamia inferens--rice swarming caterpillar

Spodoptera littoralis--Egyptian cotton leafworm

Spodoptera spp.--armyworms

Synanthedon spp.--clearwing moths

Trichoplusia ni--cabbage looper

Tryporyza incertula--yellow rice borer

Crambus spp.--webworms

Orthoptera

Blatella spp.--cockroaches

Gryllus spp.--field crickets

Melanoplus spp.--grasshoppers

Periplaneta spp.--cockroaches

Scapteriscus acletus--southern mole cricket

Thysanoptera

Frankliniella tritici--flower thrips

Sericothrips variabilis--soybean thrips

Thrips simplex--gladiolus thrips

Thrips tabaci--onion thrips

and among the arachnids, the following:

    ______________________________________                                         Family   Scientific Name   Common Name                                         ______________________________________                                         ACARIDAE                                                                                Aleurobius farinae                                                                               Flour mite                                                   Rhizoglyphus echinopus                                                                           Bulb mite                                                    Rhizoglyphus elongatus                                                                           Elongate mite                                                Rhizoglyphus rhizophagus                                                                         Root mite                                                    Rhizoglyphus sagittatae                                                                          Balsam root mite                                             Rhizoglyphus tarsalis                                                                            Beet mite                                           ERIO-                                                                          PHYIDAE                                                                                 Abacarus hystrix                                                               Aceria brachytarsus                                                            Aceria essigi     Redberry mite                                                Aceria ficus                                                                   Aceria fraxinivorus                                                            Aceria granati                                                                 Aceria parapopuli Cottonwood mite                                              Aceria sheldoni   Citrus bud mite                                              Aceria tulipae    Wheat curl mite                                              Aceria schlechtendali                                                                            Apple rust mite                                              Eriophyes convolvens                                                           Eriophyes insidiosus                                                           Eriophyes malifoliae                                                                             Apple leaf mite                                              Eriophyes padi    Plum twig gall                                                                 mite                                                         Eriophyes pruni   Plum leaf gall                                                                 mite                                                         Eriophyes pyri    Pear leaf                                                                      blister mite                                                 Eriophyes ramosus Juniper mite                                                 Eriophyes ribis   Currant gall mite                                            Eriophyes vitis   Grape erineum mite                                           Phyllocoptes gracilis                                                                            Blackberry mite                                              Phyllocoptruta oleivora                                                                          Citrus rust mite                                             Phytoptus ribis                                                                Trisetacus pini   Pine needle mite                                             Vasates amygdalina                                                                               David peach mite                                             Vasates cornutus  Peach silver mite                                            Vasates eurynotus Celery rust mite                                             Vasates schlechtendali                                                                           Rusty leaf mite                                     EUPO-                                                                          DIDAE                                                                                   Linopodes spp.                                                        PENTHA-                                                                        LEIDAE                                                                                  Halotydeus destrustor                                                                            Redlegged earth                                                                mite                                                                           Black sand mite                                              Penthaleus major  Winter grain mite                                                              Blue oat mite                                       PYEMO-                                                                         TIDAE                                                                                   Siteroptes cerealium                                                  TARSO-                                                                         NEMIDAE                                                                                 Polyphagotarsonemus latus                                                                        Broad mite                                                   Steneotarsonemus pallidus                                                                        Cyclamen mite                                       TENUI-                                                                         PALPIDAE                                                                                Brevipalpus californicus                                                                         California                                                                     citrus mite                                                  Brevipalpus obovatus                                                           Brevipalpus lewisi                                                                               Flat mite                                                    Tenuipalpes granati                                                            Tenuipalpes pacificus                                                 TETRA-                                                                         NYCHIDAE                                                                                Bryobia arborea   Brown mite                                                   Bryobia rubrioculus                                                            Eotetranychus coryli                                                           Eotetranychus lewisi                                                                             Lewis spider                                                                   mite                                                         Eotetranychus sexmaculatus                                                                       Sixspotted                                                                     spider mite                                                  Eotetranychus weldoni                                                                            Weldon's mite                                                Eotetranychus willametti                                                       Eutetranychus banksi                                                                             Texas citrus                                                                   mite                                                         Mediolata mali    Apple mite                                                   Oligonychus ilicis                                                                               Southern red                                                                   mite                                                         Oligonychus pratensis                                                                            Banks grass mite                                             Oligonychus ununguis                                                                             Spruce tree                                                                    spider mite                                                  Panonychus citri  Citrus red mite                                              Panonychus ulmi   European red mite                                            Paratetranychus modestus                                                                         Corn mite                                                    Paratetranychus pratensis                                                                        Date mite                                                    Paratetranychus viridis                                                                          Green mite                                                   Petrobia decepta  Barley mite                                                  Schizotetranychus celarius                                                                       Bamboo mite                                                  Schizotetranychus pratensis                                                                      Alfalfa mite                                                 Tetranychus canadensis                                                                           Fourspotted mite                                             Tetranychus cinnabarinus                                                       Tetranychus mcdanieli                                                                            McDaniel mite                                                Tetranychus pacificus                                                                            Pacific mite                                                 Tetranychus schoenei                                                                             Schoene mite                                                 Tetranychus telarius                                                                             Common red spider                                            Tetranychus urticae                                                                              Twospotted                                                                     spider mite                                                  Tetranychus turkestani                                                                           Strawberry mite                                              Tetranychus desertorum                                                                           Desert mite                                         ______________________________________                                    

The present compounds are employed for the control of insects and arachnids in accordance with standard practices of the agricultural chemical industry. Thus, the compounds, while they can be employed alone, are preferably formulated with conventional adjuvants, as described in more detail in the section below concerning Formulations. The amount of the present compounds which will provide insecticidal and/or arachnicidal activity is not critical and will vary widely, depending on the locus (foliage, soil, etc.), the susceptibility of the particular insect or arachnid, the particular compound chosen, weather and soil conditions, and the like. In general, when employing the compounds in spray formulations to be applied to foliage, concentrations of from 1 to 5000 ppm are efficacious; however, lesser concentrations such as from 1 to 100 ppm are often equally efficacious. In the case of application to soil to control soil-dwelling organisms, concentrations in the soil of from 1 ppm or less to as much as 50 ppm provide good activity. With the more active members of the series, lesser concentrations of from 1 to 10 ppm provide good activity.

Application of the compounds of the present invention is by conventional practices. Where the compounds are employed for the control of corn rootworm and other soil dwelling organisms that attack roots of plants, it is often preferred to apply a compound in a band along and including the crop row. This maximizes the protection of the crop, while minimizing the total amount of compound applied. Also, since the compounds of the present invention exhibit some phytotoxicity, it is preferred that the compounds be employed in a technique by which a pesticide is prevented from contacting seeds, for example, post presswheel placement.

Preferred Embodiments

Although the compounds of the present invention are generally effective for the control of numerous insect and arachnid species, they have been found to be exceptionally effective for the control of the larval stage of corn rootworm (Diabrotica spp.) Therefore, a preferred embodiment of the present invention is a method of inactivating a corn rootworm larva which comprises applying to a locus of the larva an effective amount of a present compound.

In addition to this preferred embodiment in the identity of the insects or arachnids controlled by the present invention, there are preferred embodiments among the compounds of the present invention.

The preferences among compounds of all of formulae I, II, and III are

(1) a preference for R³ =hydrogen,

(2) a preference for R⁴ =substituted aryl as defined, more particularly, for R⁴ =substituted phenyl as defined, and especially for the following substituted phenyl groups:

(a) 2,4-disubstituted phenyl of the formula ##STR9## wherein R⁸ =chloro, bromo, iodo, cyano, methyl, trifluoromethyl, or nitro; and

(b) 2,4,5(or 2,4,6)-trisubstituted phenyl of the formula ##STR10## wherein R¹¹ =bromo, chloro, or methyl. The preferences among compounds of formula I are

(1) R⁰ =fluoro and

(2) each of R¹ and R² =CF₃, C₂ F₅, or C₃ F₇.

Among the salts of the present invention, it has been found that the ammonium salts are preferred, and among the ammonium salts, the following particular salts are especially advantageous: hexadecyltrimethylammonium, octadecyltrimethylammonium, tributylammonium, tris(2-hydroxyethyl)ammonium, tris(2 or 3-hydroxypropyl)ammonium, and dimethylbis(C₁₀ -C₁₈)ammonium.

Herbicidal Activity

In addition to exhibiting activity against insects and arachnids, the present compounds also exhibit some herbicidal activity. In general, the herbicidal activity is expressed at rates higher than those at which insecticidal and arachnicidal activity is exhibited. Therefore, the preferred insecticidal/arachnicidal utility of the present invention can generally be practiced with minimal or no phytotoxicity.

Representative compounds of the present invention were evaluated for herbicidal efficacy in standard screening tests. In these tests, each compound was evaluated against a number of crop and weed species, for both preemergent and postemergent effect. Each compound was formulated by dissolving it in the acetone/emulsifier composition described in the mite-insect screen above. It was then sprayed onto flats within one day after they had been seeded to various plant species (the preemergent test) or onto young plants about 9 days after planting (the postemergent test). Throughout the test, the pots were maintained under good greenhouse growing conditions. Ratings were made 18 days after compound application in the preemergence test, and 14 days after compound application in the postemergent test, employing a scale of 1-5, with 1=no injury and 5=death. Results were as set forth in the following tables of preemergent data (Table XIV) and postemergent data (Table XV).

The following code was used in Tables XIV and XV:

    ______________________________________                                         A = Corn           N = Large Crabgrass                                         B = Cotton         O = Mustard                                                 C = Soybean        P = Pigweed                                                 D = Wheat          Q = Ryegrass                                                E = Alfalfa        R = Small Crabgrass                                         F = Sugar Beet     S = Foxtail Millet                                          G = Rice           T = Bindweed                                                H = Cucumber       U = Wild Oat                                                I = Tomato         V = Nutgrass                                                J = Barley         W = Velvetleaf                                              K = Barnyard Grass X = Jimsonweed                                              L = Lambsquarter   Y = Smartweed                                               M = Cocklebur      Z = Morningglory                                                               a = Zinnia                                                  ______________________________________                                          Note:                                                                          8 lb/A = 8.96 kilograms per hectare (kg/ha)                                    4 lb/A = 4.48 kg/ha                                                            2 lb/A = 2.24 kg/ha                                                            1 lb/A = 1.12 kg/ha                                                            0.5 lb/A = 0.56 kg/ha                                                          0.25 lb/A = 0.28 kg/ha                                                         0.125 lb/A = 0.14 kg/ha                                                        0.0625 lb/A = 0.07 kg/ha.                                                

                                      TABLE XIV                                    __________________________________________________________________________     PLANT SPECIES                                                                  EX. Rate Pre-emergence                                                         NO. lbs/A                                                                               A B C D E F G H I J K L M N O P Q R S T U V W X Y Z a                 __________________________________________________________________________     1   8                    5   5     5 5 5     5   5   5     5 5                     4    1 1 1 3 5 5 2 3 3   3 4   4 3 4         4                                                                              3   5 3      3                                                                         4                         2    1 1 1 1 5 5 1 1 2   3 4   3 1 4         3                                                                              2   2 2      1                                                                         2                         1    1 1 1 1 3 2 1 1 1   1 3   2 1 3         1                                                                              1   1 1      1                                                                         1                     4   8                    5   5     5 5 5         5                                                                              5   5        5                                                                         5                         4    5 4 5 5   5 5       5     5 5 5         5                                                                              5   5 5      5                                                                         5                         2    5 4 5 5   5 4       5     5 4 5         5                                                                              5   5 4      5                                                                         4                         1    4 3 4 4   5 4       5     5 3 5         4                                                                              3   4 3      5                                                                         3                         .5   2 3 4 1   3 1   2 1   2   2 2 4         3                                                                              1   2 2      4                    .25  2 2 3 1   4 1   1 1   2   1 2 3         3                                                                              1   2 2      3                    .125 1 1 3 1   2 1   1 1   1   1 1 2         1                                                                              1   1 1      2                    .0625                                                                               1 1 1 1   2 1   1 1   1   1 1 1         1                                                                              1   1 1      1                5   8                    5   4     5 5 5         5                                                                              5   5        3                                                                         3                         4    1 1 2 3   5 3       2     5 3 5         4                                                                              3   2 4      2                                                                         3                         2    1 1 1 1   3 1       1     1 1 3         1                                                                              1   1 1      1                                                                         1                         1    1 1 1 1   1 1       1     1 1 3         1                                                                              1   1 1      1                                                                         1                     6   8                    4   5     5 4 5         5                                                                              5   5        5                                                                         4                         4    5 5 5 5   5 5       5     5 5 5         5                                                                              5   5 5      5                                                                         5                         2    5 5 5 5   5 5       5     5 5 5         5                                                                              5   5 5      5                                                                         5                         1    5 3 5 5   5 5       5     5 4 5         5                                                                              5   5 4      5                                                                         5                         .5   3 1 4 1   3 1   2 1   3   3 2 3         4                                                                              1   3 1      4                    .25  2 1 4 1   3 1   2 1   3   3 1 3         3                                                                              1   2 1      4                    .125 1 1 3 1   1 1   1 1   1   1 1 2         3                                                                              1   1 1      4                    .0625                                                                               1 1 2 1   1 1   1 1   1   1 1 1         1                                                                              1   1 1      2                7   8                    3   5     3 3 4         5                                                                              3   5        5                                                                         3                         4    3 2 4 2   4 4       3     4 3 4         3                                                                              4   5 2      4                                                                         4                         2    2 1 4 1   3 3       1     3 1 4         2                                                                              1   1 1      3                                                                         2                         1    1 1 1 1   1 1       1     2 1 3         2                                                                              1   1 1      1                                                                         1                     8   8                    5   5     5 5 5         5                                                                              5   5        5                                                                         5                         4    4 3 5 5   5 5       4     5 5 5         5                                                                              4   5 4      4                                                                         5                         2    3 3 5 4   5 5       4     5 5 5         5                                                                              4   5 4      4                                                                         5                         1    2 2 4 2   5 4       3     5 5 5         4                                                                              5   3 2      3                                                                         2                         .5   1 3 2 2   3 2   2 1   1   3 2 2         1                                                                              1   2 1      4                    .25  1 1 1 1   2 1   1 1   1   1 1 1         1                                                                              1   1 1      1                    .125 1 1 1 1   1 1   1 1   1   1 1 1         1                                                                              1   1 1      1                    .0625                                                                               1 1 1 1   1 1   1 1   1   1 1 1         1                                                                              1   1 1      1                9   8                    1   1     3 1 1         1                                                                              1   1        1                                                                         1                     10  8                    1   1     5 1 5         4                                                                              1   1        1                                                                         1                         4    1 1 1 1   1 1       1     1 1 4         3                                                                              1   1 1      1                                                                         1                         2    1 1 1 1   1 1       1     1 1 3         1                                                                              1   1 1      1                                                                         1                         1    1 1 1 1   1 1       1     1 1 3         1                                                                              1   1 1      1                                                                         1                     11  8                    1   1     1 1 1         1                                                                              1   1        1                                                                         1                     13  8                    5   5     5 5 5         5                                                                              5   5        5                                                                         5                         4    1 1 3 3 5 5 3 4 2   3 5   4 3 4         5                                                                              3   4 2      2                                                                         2                         2    1 2 3 4 5 4 2 3 2   3 5   4 3 4         4                                                                              1   3 2      3                                                                         2                         1    1 1 3 3 5 4 2 3 1   2 5   4 3 3         4                                                                              2   3 1      2                                                                         1                         .5   1 1 2 1   3 1   2 1   5   3 1 4         3                                                                              2   1 1      2                    .25  1 1 1 1   4 1   1 1   2   3 1 4         3                                                                              1   1 1      1                    .125 1 1 1 1   1 1   1 1   1   1 1 1         1                                                                              1   1 1      1                    .0625                                                                               1 1 1 1   1 1   1 1   1   1 1 1         1                                                                              1   1 1      1                14  8        1           1 1       1 1 1         1            1                15  8        1           2 1       4 3 5         2            3                    4    1 1 1 1   1 1   2 1   2   1 2 2         1                                                                              1   1 2      1                    2    1 1 1 1   1 1   1 1   1   1 1 1         1                                                                              1   1 1      1                    1    1 1 1 1   1 1   1 1   1   1 1 1         1                                                                              1   1 1      1                    .5   1 1 1 1   1 1   1 1   1   1 1 1         1                                                                              1   1 1      1                16  8        5           5 4       4 5 5         5            5                    4    3 2 4 2   5 3   4 2   5   5 5 5         5                                                                              4   4 3      5                    2    3 2 4 2   5 3   4 2   5   3 5 5         5                                                                              2   4 2      5                    1    2 1 3 1   5 2   4 1   5   4 2 5         5   5 2      4                    .5   1 1 1 1   1 1   1 1   5   1 1 1         1                                                                              1   1 1      1                17  8        4           5 4       5 5 5         5            5                    4    3 3 3 2   5 3   5 3   5   5 5 5         5                                                                              5   5 5      4                    2    2 2 3 2   5 3   5 3   5   5 4 5         5                                                                              4   4 4      3                    1    1 1 2 2   5 2   4 2   5   4 2 5         5                                                                              3   4 1      2                    .5   1 1 1 1   4 1   3 1   4   4 1 4         1                                                                              1   1 1      1                18  8        1           4 2       5 4 5         5            2                    4    1 2 1 1   4 4   1 1   3   2 4 3         2                                                                              1   1 1      3                    2    1 1 1 1   4 3   1 1   3   2 1 1         1                                                                              1   1 1      1                    1    1 1 1 1   1 1   1 1   1   1 1 1         1                                                                              1   1 1      1                    .5   1 1 1 1   1 1   1 1   1   1 1 1         1                                                                              1   1 1      1                19  8        1           1 1       5 3 5         5            2                    4    1 1 1 1   4 1   3 1   3   3 1 5         1                                                                              1   1 1      1                    2    1 1 1 1   3 1   3 1   3   3 1 5         1                                                                              1   1 1      1                    1    1 1 1 1   2 1   2 1   1   3 1 4         1                                                                              1   1 1      1                    .5   1 1 1 1   2 1   1 1   1   1 1 2         1                                                                              1   1 1      1                20  8        1           4 1       2 2 3         5            3                    4    1 1 1 1   5 1   2 1   2   2 4 3         3                                                                              1   2 3      1                    2    1 1 1 1   1 1   1 1   1   1 1 1         1                                                                              1   1 1      1                    1    1 1 1 1   1 1   1 1   1   1 1 1         1                                                                              1   1 1      1                    .5   1 1 1 1   1 1   1 1   1   1 1 1         1                                                                              1   1 1      1                21  8        5           5 5       5 5 5         5            5                    8        2           5 3       5 5 5         5            4                    4    2 1 2 2   5 3   5 3   5   5 4 5         5                                                                              4   5 4      5                    4    1 1 2 1   5 1   4 1   5   1 4 4         1                                                                              1   3 1      1                    2    1 1 4 3   5 3   4 3   5   4 2 4         5                                                                              3   3 4      4                    2    1 1 1 1   3 1   3 1   2   1 3 2         1                                                                              1   1 1      1                    1    1 1 2 1   5 1   2 2   3   4 1 4         3                                                                              2   3 2      3                    1    1 1 1 1   1 1   1 1   1   1 1 1         1                                                                              1   1 1      1                    .5   1 1 1 1   4 1   2 1   3   1 1 3         1                                                                              1   1 1      1                    .5   1 1 1 1   1 1   1 1   1   1 1 1         1                                                                              1   1 1      1                22  8        5           5 5       5 5 5         5            5                    4    2 2 4 3   5 3   5 3   5   5 5 5         5                                                                              5   5 4      5                    2    1 1 3 2   5 3   4 3   5   4 4 5         5                                                                              5   5 3      4                    1    1 1 2 2   5 3   3 2   5   3 2 4         3                                                                              2   4 2      4                    .5   1 1 1 1   5 3   3 2   4   2 1 4         4                                                                              2   2 1      2                23           2           2 1       2 3 3         4            1                24  8                    5   5     5 5 5         5                                                                              5   5        5                                                                         5                         4    1 3 4 4 5 5 4 5 5   2 4   4 4 4         5                                                                              4   5 3      4                                                                         3                         2    1 2 3 3 5 5 3 3 5   2 4   5 5 4         4                                                                              3   4 2      2                                                                         2                         1    1 1 1 1 4 3 2 2 1   1 4   4 4 4         4                                                                              1   2 1      2                                                                         1                         1    1 1 1 1 3 3 1 2 1   1 4   2 4 5         1                                                                              1   1 1      1                                                                         1                         .5   1 1 1 1 2 1 1 2 1   1 3   1 1 1         1                                                                              1   1 1      1                                                                         1                         .25  1 1 1 1 2 1 1 1 1   1 3   1 1 1         1                                                                              1   1 1      1                                                                         1                     25  8                    5   5     5 5 5         5                                                                              5   5        5                                                                         5                         4    3 3 3 5 5 5 4 5 4   3 5   4 5 5         5                                                                              3   5 5      5                                                                         5                         2    1 2 3 3 5 5 4 4 3   5 5   3 3 4         5                                                                              2   5 3      5                                                                         3                         1    2 1 2 5 5 5 3 3 4   3 5   1 2 5         5                                                                              2   3 3      3                                                                         2                         1    1 1 1 1 4 5 3 3 2   1 5   2 4 4         5                                                                              2   4 3      4                                                                         1                         .5   1 1 1 3 3 1 1   1   1 4   1 3 3         1                                                                              1   1 1      1                                                                         1                         .2   1 1 1 1 1 1 1 1 1   1 2   1 2 2         1                                                                              1   1 1      1                                                                         1                     26  8                    5   5     5 5 5         5                                                                              5   5        5                                                                         5                         4    3 5 5 5 5 5 5 5 5   4 5   5 5 5         5                                                                              5   5 5      5                                                                         5                         2    2 3 5 4 5 5 3 3 2   3 5   4 5 5         5                                                                              3   5 4      3                                                                         2                         1    2 2 1 4 4 5 3 3 2   2 4   1 3 4         2                                                                              3   3 3      1                                                                         4                         1    1 2 4 3 5 5 2 3 2   2 5   3 4 5         5                                                                              3   4 2      4                                                                         2                         .5   1 1 1 3 2 1 1 1 1   1 4   1 2 3         1                                                                              1   1 1      1                                                                         1                         .25  1 1 1 1 1 1 1 1 1   1 4   1 1 1         1                                                                              1   1 1      1                                                                         1                     27  8                    5   5     5 5 5         5                                                                              5   5        5                                                                         5                         8                    5   5     5 5 5         5                                                                              5   5        5                                                                         5                         8                    5   4     5 5 5         5                                                                              5   5        5                                                                         5                         4    2 3 4 5 5 5 5 5 4   3 5   4 5 5         5                                                                              5   5 5      5                                                                         5                         4    1 1 1 2 5 5 2 2 2   3 4   3 5 4         5                                                                              4   3 3      2                                                                         4                         2    1 1 2 5 5 5 5 5 4   2 5   3 4 5         5                                                                              2   5 2      5                                                                         4                         2    1 1 1 5 5 5 2 4 2   2 4   3 4 4         4                                                                              2   2 2      4                                                                         1                         1    1 1 2 3 3 5 1 4 3   1 4   3 3 5         4                                                                              2   3 1      3                                                                         2                         1    1 1 1 1 2 4 1 2 2   2 5   1 1 4         1                                                                              1   1 1      2                                                                         1                     28  8                    5   4     5 5 5         5                                                                              5   4        5                                                                         4                         4    1 1 1 1 5 5 3 3 3   2 5   3 4 5         5                                                                              4   5 4      4                                                                         4                         2    1 1 1 2 5 5 2 2 2   2 5   3 2 4         3                                                                              3   4 4      5                                                                         2                         1    1 1 1 1 5 4 1 2 1   1 5   1 3 4         3                                                                              1   3 2      1                                                                         1                     29  8                    4   4     4 5 4         5                                                                              4   5        4                                                                         4                         8        3           5 4       5 5 5         5            5                    4    1 1 1 4 5 5 3 3 4   3 5   3 5 4         5                                                                              3   3 5      2                                                                         3                         2    1 1 1 2 2 5 2 2 3   3 4   1 3 4         4                                                                              2   2 4      2                                                                         2                         1    1 1 1 1 1 3 1 1 1   1 1   1 1 4         1                                                                              1   1 1      1                                                                         1                     30  8                    5   3     4 4 5         5                                                                              4   5        5                                                                         4                         4    2 1 1 2 5 5 1 2 3   3 4   3 4 5         5                                                                              3   3 2      2                                                                         4                         2    1 1 1 2 2 3 1 2 2   2 5   1 1 5         5                                                                              2   1 1      2                                                                         3                         1    1 1 1 2 2 2 1 1 1   2 1   1 1 5         3                                                                              1   1 1      1                                                                         1                     32  8                    5   5     5 5 5         5                                                                              5   5        5                                                                         5                         4    2 2 3 4 5 5 5 4 5   3 5   4 5 4         5                                                                              5   5 5      4                                                                         3                         2    1 1 1 4 5 5 3 4 4   3 4   3 4 4         4                                                                              4   4 3      3                                                                         2                         1    1 1 1 1 1 3 3 3 2   2 1   1 1 5         2                                                                              1   1 2      1                                                                         1                     34  8                    4   1     4 2 5         4                                                                              2   2        2                                                                         2                         4    1 1 3 1   5 3       3     5 2 5         5                                                                              3   1 4      1                                                                         1                         2    1 1 1 1   5 3       3     5 3 5         4                                                                              3   1 1      1                                                                         1                         1    1 1 1 1   5 2       3     3 1 5         1                                                                              2   1 1      1                                                                         1                     36  8                    5   5     5 5 5         5                                                                              5   5        4                                                                         3                         4    4 3 5 4   5 5       5     5 5 5         5                                                                              5   5 5      5                                                                         4                         2    3 1 3 2   5 5       5     5 4 5         5                                                                              5   4 5      3                                                                         3                         1    1 1 3 1   5 1       1     4 1 4         3                                                                              1   2 2      1                                                                         1                     38  8        1           2 1       2 1 4         4            1                    8        1           2 1       2 1 4         4            1                    4    1 1 1 1   1 1   2 1   5   3 1 3         1                                                                              1   1 1      1                    2    1 1 1 1   1 1   1 1   1   1 1 1         1                                                                              1   1 1      1                    1    1 1 1 1   1 1   1 1   1   1 1 1         1                                                                              1   1 1      1                    .5   1 1 1 1   1 1   1 1   1   1 1 1         1                                                                              1   1 1      1                39  8        1           1 1       1 1 1         1            1                    8        1           1 1       1 1 1         1            1                41  8                    5 1       2 5 5         3            3                    4    1 1 1 1   4 1   5 2   5   1 5 5         1                                                                              2   4 2      1                    2    1 1 1 1   5 1   3 1   4   1 3 3         1                                                                              1   1 1      1                    1    1 1 1 1   1 1   1 1   1   1 1 1         1                                                                              1   1 1      1                    .5   1 1 1 1   1 1   1 1   1   1 1 1         1                                                                              1   1 1      1                43  8        3           1 1       1 1 1         1            1                44  8        3           1 1       1 4 4         1            1                    4    2 2 3 1   2 2   1 1   5   1 1 5         1                                                                              1   1 1      1                    2    1 1 2 1   1 1   1 1   4   1 1 2         1                                                                              1   1 1      1                    1    1 1 1 1   1 1   1 1   1   1 1 1         1                                                                              1   1 1      1                    .5   1 1 1 1   1 1   1 1   1   1 1 1         1                                                                              1   1 1      1                45  8        1           1 1       1 1 1         1            1                47  8        1           5 2       5 5 5         5            3                    4    3 2 1 1   5 2   2 2   5   2 2 3         3                                                                              3   1 3      1                    2    1 1 1 1   4 1   3 1   5   2 1 5         2                                                                              2   1 1      1                    1    1 1 1 1   1 1   1 1   1   1 1 1         1                                                                              1   1 1      1                    .5   1 1 1 1   1 1   1 1   1   1 1 1         1                                                                              1   1 1      1                49  8        2           5 2       5 4 5         5            5                    4    3 1 1 3   5 2   5 3   5   2 5 5         5                                                                              5   4 5      3                    2    3 1 1 1   5 2   3 1   5   1 5 5         5                                                                              3   2 3      1                    1    2 1 1 1   5 1   1 1   5   2 1 3         4                                                                              3   1 1      1                    .5   1 1 1 1   4 1   1 1   5   1 1 3         1                                                                              1   1 1      1                50  8        2           5 2       5 4 5         5            3                    4    4 1 3 3   5 2   5 3   5   4 5 5         5                                                                              3   3 4      3                    2    3 1 2 3   5 1   3 2   5   3 3 3         3                                                                              3   2 3      3                    1    3 1 1 2   3 1   2 1   5   2 1 3         2                                                                              2   1 1      2                    .5   1 1 1 1   1 1   1 1   1   1 1 1         1                                                                              1   1 1      1                51  8        1           5 1       5 4 5         5            3                    4    2 1 3 3   5 1   4 2   5   5 4 5         5                                                                              4   4 3      2                    2    1 1 1 1   3 1   1 1   2   3 2 3         5                                                                              4   3 1      3                    1    1 1 1 1   1 1   1 1   1   1 1 3         4                                                                              1   2 1      3                    .5   1 1 1 1   1 1   1 1   1   2 1 1         3                                                                              1   1 1      1                __________________________________________________________________________

                                      TABLE XV                                     __________________________________________________________________________     PLANT SPECIES                                                                  Post-emergence                                                                 EX. Rate                                                                       NO. lbs/A                                                                               A B C D E F G H I J K L M N 0 P Q       R                                                                              S                                                                              T                                                                              U V W X Y    Z                                                                         a                     __________________________________________________________________________      1  8                    5   5     5 5 5     5   5   5     5 5                     4                    5   5     5 5 5         5                                                                              5   5        5                                                                         5                         2                    5   3     2 5 4         4                                                                              3   4        4                                                                         5                         1                    5   4     3 5 4         4                                                                              3   5        4                                                                         5                         1                    5   1     1 5 4         3                                                                              1   4        2                                                                         5                         .5                   5   1     1 5 3         3                                                                              1   2        1                                                                         5                         .25                  3   1     1 4 3         2                                                                              1   1        1                                                                         3                      4  8                    5   5     5 5 5         5                                                                              5   5        5                                                                         5                         4                    5   5     5 5 5         5                                                                              4   5        5                                                                         5                         2                    5   5     5 5 5         5                                                                              4   5        5                                                                         5                         1                    5   5     4 5 5         5                                                                              4   4        4                                                                         5                         .5   3 2 3 3   4 2   5 2   5   5 5 5         5                                                                              3   2 5      3                    .25  4 1 2 2   3 1   4 1   5   4 5 5         3                                                                              2   2 4      1                    .125 4 1 2 1   3 1   2 1   5   3 4 4         3                                                                              1   1 2      1                    .0625                                                                               2 1 2 1   1 1   1 1   4   1 4 3         1                                                                              1   1 1      1                 5  8                    5   4     5 5 5         4                                                                              2   3        4                                                                         5                         4                    5   2     2 5 3         3                                                                              2   3        3                                                                         4                         2                    5   2     2 5 3         3                                                                              1   2        3                                                                         3                         1                    3   1     1 4 2         2                                                                              1   2        2                                                                         3                      6  8                    5   5     5 5 5         5                                                                              5   5        5                                                                         5                         4                    5   5     5 5 5         5                                                                              5   5        4                                                                         5                         2                    5   5     5 5 5         5                                                                              5   5        4                                                                         5                         1                    5   5     5 5 4         5                                                                              5   5        4                                                                         5                         .5   5 4 3 2   3 2   5 1   5   5 5 4         5                                                                              3   4 5      2                    .25  4 1 2 2   2 1   5 1   4   5 4 4         5                                                                              3   3 5      2                    .125 5 1 2 2   2 1   4 1   4   2 4 3         4                                                                              2   3 4      2                    .0625                                                                               5 1 1 1   1 2   1 1   4   2 3 3         1                                                                              1   1 1      1                 7  8                    5   3     3 4 3         5                                                                              3   5        4                                                                         4                         4                    5   5     3 5 3         3                                                                              2   3        3                                                                         4                         2                    4   3     2 5 3         3                                                                              1   3        2                                                                         3                         1                    1   1     1 3 2         3                                                                              1   1        1                                                                         1                      8  8                    5   4     5 5 5         5                                                                              5   5        4                                                                         5                         4                    5   5     4 5 4         5                                                                              3   5        4                                                                         5                         2                    5   5     3 5 3         5                                                                              4   5        4                                                                         5                         1                    5   5     3 5 3         5                                                                              4   5        4                                                                         5                         .5   2 1 3 2   4 2   5 2   5   1 5 1         2                                                                              2   3 5      2                    .25  1 1 2 2   1 1   4 1   5   1 5 1         1                                                                              1   1 3      1                    .125 1 1 2 1   1 1   1 1   3   1 4 1         1                                                                              1   1 1      1                    .0625                                                                               1 1 1 1   1 1   1 1   1   1 1 1         1                                                                              1   1 1      1                 9  8                    5   3     4 5 4         2                                                                              4   4        4                                                                         5                         4                    1   1     1 1 1         1                                                                              1   1        1                                                                         1                         2                    1   1     1 1 1         1                                                                              1   1        1                                                                         1                         1                    1   1     1 1 1         1                                                                              1   1        1                                                                         1                     10  8                    4   3     4 5 4         4                                                                              3   4        4                                                                         5                         4                    2   1     1 4 2         3                                                                              1   2        2                                                                         2                         2                    1   1     1 3 1         2                                                                              1   1        1                                                                         1                         1                    1   1     1 1 1         1                                                                              1   1        1                                                                         1                     11  8                    4   2     2 5 4         4                                                                              1   3        2                                                                         4                         4                    3   1     1 3 2         3                                                                              1   3        2                                                                         4                         2                    2   1     1 3 1         4                                                                              1   2        1                                                                         1                         1                    1   1     1 2 1         3                                                                              1   2        1                                                                         1                     13  8                    5   5     5 5 5         5                                                                              5   5        5                                                                         5                         4                    5   5     5 5 5         5                                                                              5   5        5                                                                         5                         2                    5   4     5 5           5                                                                              4   5        5                                                                         5                         2                    4   2     4 5 5         3   1        2                                                                         5                         1                    5   4     5 5           5                                                                              4   5        4                                                                         5                         1                    5   3     5 5 5         5                                                                              5   5        4                                                                         5                         .5   3 2 4 2   5 2   5 2   5   2 5 5         5                                                                              3   4 5      3                    .5                   5   4     5 5 5         5                                                                              4   5        4                                                                         5                         .25  4 2 2 2   4 1   4 1   5   3 5 5         3                                                                              3   2 5      3                    .25                  5   3     4 5 4         5                                                                              2   5        2                                                                         5                         .125 2 1 2 2   3 1   2 1   5   3 5 4         3                                                                              3   2 2      2                    .125                 4   2     4 5 4         5                                                                              1   1        2                                                                         5                         .0625                                                                               1 1 2 1     1   1 1   5   4 3 4         2                                                                              2   1 1      1                    .0625                1   1     2 3 2         3                                                                              1   1        1                                                                         4                     14  8        1           1 1       1 1 1         1            1                15  8        3           5 2       3 5 5         3            3                    4    2 1 2 1   2 1   4 1   3   4 4 5         2                                                                              1   2 2      1                    2    1 1 2 1   1 1   1 1   3   2 3 3         1                                                                              1   1 1      1                    1    1 1 1 1   1 1   1 1   1   1 1 1         1                                                                              1   1 1      1                    .5   1 1 1 1   1 1   1 1   1   1 1 1         1                                                                              1   1 1      1                16  8        5           5 4       5 5 5         5            5                    4    3 3 4 3   5 2   5 3   5   5 5 5         5                                                                              4   5 5      4                    2    4 2 3 2   5 2   5 2   5   3 5 5         5                                                                              4   3 5      4                    1    3 2 2 2   4 2   5 1   5   3 5 5         5                                                                              4   2 5      4                    .5   3 2 2 1   4 1   5 1   5   2 5 4         3                                                                              2   1 3      4                17  8        4           5 4       5 5 5         5            4                    4    4 4 4 4   5 3   5 4   5   4 5 5         5                                                                              4   4 5      4                    2    4 4 4 4   5 4   5 4   5   4 5 4         5                                                                              4   4 5      4                    1    4 3 4 4   5 3   5 4   5   3 5 4         5                                                                              4   3 5      4                    .5   4 2 3 2   5 3   5 3   5   2 4 3         3                                                                              1   2 5      3                18  8        3           5 3       3 5 5         2            4                    4    2 4 2 2   4 2   3 2   5   2 5 5         2                                                                              1   1 5                           2    2 3 2 1   1 2   1 1   3   2 3 3         2                                                                              1   1 3                           1    1 2 2 1   2 2   1 1   3   1 3 2         1                                                                              1   1 2                           .5   1 2 2 1   1 1   1 1   1   1 1 1         1                                                                              1   1 1                       19  8        2           4 2       4 5 5         4            3                    4    3 3 3 3   4 2   5 2   5   3 4 5         3                                                                              2   3 4      4                    2    3 2 2 2   4 2   4 1   5   3 3 5         3                                                                              2   2 3      3                    1    3 2 1 1   4 2   3 1   5   2 3 3         3                                                                              1   1 3      2                    .5   3 2 1 1   4 2   1 1   4   1 2 2         2                                                                              1   1 2      1                20  8        3           5 2       2 5 5         5            4                    4    2 2 3 1   5 1   5 2   5   3 5 4         3                                                                              1   2 5      3                    2    2 2 2 1   4 1   5 1   5   2 5 4         3                                                                              1   1 5      3                    1    1 2 2 1   3 1   2 1   4   2 5 2         1                                                                              1   1 3      2                    .5   1 2 2 1   2 1   1 1   3   1 4 1         1                                                                              1   1 2      2                21  8        4           5 5       5 5 5         5            5                    8        4           5 4       5 5 5         5            5                    4    4 3 2 2   5 2   5 2   5   5 5 5         5                                                                              3   5 5      3                    4    3 5 3 2   5 2   5 2   5   5 5 5         5                                                                              4   5 5      4                    2    5 3 2 4   5 2   5 2   5   3 5 5         2                                                                              3   5 5      2                    2    4 3 2 2   5 2   5 1   5   5 5 5         5                                                                              3   5 5      3                    1    4 2 2 2   5 1   5 1   5   4 5 5         3                                                                              3   5 4      2                    1    3 2 2 2   3 1   5 1   5   5 5 5         5                                                                              1   4 5      3                    .5   3 3 2 2   4 1   5 1   5   3 3 5         2                                                                              3   2 2      2                    .5   2 2 2 1   3 1   5 1   5   3 2 4         3                                                                              1   1 3      2                22  8        5           5 5       5 5 5         5            5                    4    4 5 4 3   5 3   5 3   5   4 5 5         4                                                                              4   5 5      5                    2    4 4 4 4   5 3   5 3   5   3 5 5         3                                                                              3   5 5      5                    1    5 4 4 3   5 3   5 3   5   2 5 5         3                                                                              2   3 5      4                    .5   4 4 3 2   5 2   5 2   5   2 5 5         2                                                                              2   3 4      2                    .5   2 3 3 3   5 3   5 3   5   4 5 5         4                                                                              3   4 5      2                    .25  3 2 3 2   4 3   5 1   5   3 4 5         4                                                                              2   3 5      2                    .125 2 2 3 2   3 2   1 1   5   2 4 3         2                                                                              1   2 4      1                    .0625                                                                               1 1 2 2   2 2   1 1   3   1 3 2         1                                                                              1   1 1      1                23  8        4           5 3       5 5 5         5            4                    4    2 4 3 2   5 2   5 2   5   2 4 4         2                                                                              2   2 4      3                    2    1 2 2 1   4 1   4 1   5   2 4 3         1                                                                              1   2 3      2                    1    1 2 1 1   3 1   3 1   5   3 3 3         1                                                                              1   2 3      2                    .5   1 2 1 1   3 1   1 1   3   1 3 2         1                                                                              1   1 2      1                24  8                    5   5     5 5 5         5                                                                              5   5        5                                                                         5                         4                    5   3     4 5 5         4                                                                              5   5        4                                                                         5                         2                    5   2     4 5 4         4                                                                              2   4        4                                                                         5                         1                    5   2     3 5 3         2                                                                              3   3        2                                                                         5                         1                    5   1     2 5 5         2                                                                              2   1        2                                                                         4                         .5                   3   1     1 5 5         1                                                                              3   1        2                                                                         4                         .25                  2   1     1 3 3         1                                                                              1   1        1                                                                         2                     25  8                    5   4     5 5 5         5                                                                              5   5        5                                                                         5                         4                    5   4     5 5 5         5                                                                              5   5        4                                                                         5                         2                    5   2     5 5 5         5                                                                              5   5        4                                                                         5                         1                    5   4     4 5 4         4                                                                              3   4        3                                                                         5                         1                    5   1     5 5 5         5                                                                              5   5        2                                                                         5                         .5                   5   2       5 4         5   5        3                                                                         5                         .25                  4   2     1 5 1         3                                                                              2   4        1                                                                         4                     26  8                    5   5     5 5 5         5                                                                              5   5        4                                                                         5                         4                    5   3     5 5 5         5                                                                              5   5        5                                                                         5                         2                    5   2     5 5 4         5                                                                              5   5        4                                                                         5                         1                    5   3     2 5 3         5                                                                              4   5        2                                                                         5                         1                    5   1     5 5 4         5                                                                              5   5        3                                                                         5                         .5                   5   2     3 5           2                                                                              2   4        2                                                                         5                         .25                  4   1     1 4 2         2                                                                              2   2        1                                                                         3                     27  8                    5   5     5 5 5         5                                                                              5   5        5                                                                         5                         8                    5   5     4 5 5         4                                                                              3   4        2                                                                         5                         8                    5   4     5 5 5         5                                                                              5   5        5                                                                         5                         4                    5   3     4 5 4         5                                                                              5   5        5                                                                         5                         4                    5   4     3 5 4         5                                                                              2   5        3                                                                         5                         2                    5   2     5 5 3         5                                                                              5   3        5                                                                         5                         2                    4   4     2 5 4         4                                                                              2   3        3                                                                         5                         1                    5   2     2 5 1         5                                                                              5   5        4                                                                         5                         1                    5   3     1 5 3         3                                                                              2   3        2                                                                         3                         1                    5   2     4 5 4         5                                                                              4   3        4                                                                         5                         .5                   3   2     3 5 2         4                                                                              4   3        3                                                                         3                         .25                  2   1     1 4 1         3                                                                              4   1        2                                                                         4                     28  8                    5   4     4 5 5         4                                                                              4   5        5                                                                         5                         4                    5   2     4 5 5         5                                                                              2   5        4                                                                         5                         2                    5   2     4 5 5         5                                                                              2   3        3                                                                         5                         1                    5   1     3 5 4         5                                                                              2   3        2                                                                         5                         1                    4   4     2 5 4         5                                                                              2   4        3                                                                         5                         .5                   3   2     1 5 4         4                                                                              2   3        2                                                                         5                         .25                  3   1     1 5 1         4                                                                              1   2        2                                                                         2                     29  8                    4   4     5 5 5         5                                                                              5   5        5                                                                         5                         8        4           5 3       5 5 5         5            4                    4                    5   4     4 5 5         4                                                                              2   4        4                                                                         5                         2                    1   4     1 5 4         2                                                                              2   4        3                                                                         5                         1                    4   2     2 5 4         2                                                                              2   3        2                                                                         5                     30  8                    5   4     5 5 5         5                                                                              3   5        5                                                                         5                         4                    5   4     3 5 5         4                                                                              2   3        3                                                                         5                         2                    5   3     3 5 4         2                                                                              2   5        3                                                                         5                         1                    5   3     2 5 4         3                                                                              1   3        3                                                                         4                     32  8                    5   5     5 5 5         5                                                                              5   5        5                                                                         5                         4                    5   4     5 5 5         5                                                                              5   5        4                                                                         5                         2                    5   3     3 5 4         2                                                                              1   4        4                                                                         4                         1                    5   3     2 5 3         2                                                                              2   5        3                                                                         5                     34  8                    5   2     4 5 5         2                                                                              4   5        4                                                                         5                         4                    5   3     2 5 4         3                                                                              2   4        3                                                                         5                         2                    5   2     1 5 3         4                                                                              2   2        3                                                                         5                         1                    4   2     1 5 3         3                                                                              2   2        1                                                                         3                     36  8                    5   4     5 5 5         5                                                                              5   5        5                                                                         5                         4                    5   5     4 5 4         5                                                                              4   5        4                                                                         5                         2                    5   5     3 5 3         5                                                                              3   5        4                                                                         5                         1                    5   4     3 5 3         5                                                                              2   3        3                                                                         4                     38  8        2           3 2       2 2 3         2            3                    8        2           3 2       2 2 3         2            3                39  8        2           3 1       3 4 2         1            2                41  8        5           5 3         5 4         3            3                    4    3 3 3 3   4 2   5 3   5   5 5 5         2                                                                              2   4 5      2                    2    4 2 3 3   4 2   5 2   5   5 5 5         4                                                                              2   2 5      2                    1      2 2 2   4 1   5 2   5   3 5 3         2                                                                              2   2 3      2                    .5   3 2 2 1   4 1   3 1   5   2 5 3         1                                                                              2   1 3      3                43  8        2           1 1       1 1 1         1            1                44  8        2           2 1       2 4 3         2            3                45  8        2           2 1       1 4 1         1            2                48  8        5           5 5       5 5 5         5            5                    4    5 4 4 3   5 3   5 3   5   5 5 5         5                                                                              4   5        5                    2    5 3 3 2   5 2   5 3   5   5 5 5         5                                                                              3   5        4                    1    5 3 3 2   5 2   5 2   5   5 5 5         4                                                                              2   5        3                    .5   4 3 3 2   5 1   5 1   5   3 5 4         2                                                                              2   3        2                49  8        4           5 4       5 5 5         5            4                    4    5 4 3 3   5 4   5 3   5   5 5 5         5                                                                              4   5 5      4                    2      3 3 3   5 4   5 3   5   4 5 5         5                                                                              4   5 5      3                    1      3 3 4   4 4   5 3   5   4 5 5         4                                                                              3   4 5      3                    .5     2 2 2   3 2   5 1   5   2 5 4         5                                                                              2   3 4      2                50  8        4           5 4       5 5 5         5            5                    4    4 3 3 3   4 4   5 3   5   5 5 5         5                                                                              5   4 5      3                    2    4 3 2 2   5 3   5 3   5   5 5 5         3                                                                              4   3 5      3                    1    5 2 2 2   3 2   5 2   5   3 5 4         4                                                                              2   2 5      2                    .5   4 1 2 1   2 2   3 1   4   1 3 3         2                                                                              1   1 2      2                54  8        3           5 4       5 5 5         5            4                    4    5 3 3 4   4 3   5 4   5   5 5 5         5                                                                              2   4 5      3                    2    4 3 3 3   5 3   5 3   5   5 5 5         4                                                                              2   4 5      2                    1      2 3 3   5 3   5 3   5   4 5 5         4                                                                              3   2 3      2                    .5   4 2 2 2   3 2   2 2   4   3 5 5         3                                                                              2   2 3      2                __________________________________________________________________________

As the foregoing illustrates, the compounds of the present invention exhibit herbicidal activity at rates of from 0.05 to 8 lbs/acre. Therefore, in another embodiment, the present invention is directed to a method for inhibiting the growth of a plant which comprises applying to the plant an effective amount of a compound of the present invention. The compounds can be applied pre-emergently for the control of germinating seeds or post-emergently for the control of existing vegetation. The compounds are preferably formulated as described below.

Other Utilities

Compounds of the present invention have exhibited nematocidal, fungicidal, anthelmintic, and ectoparasiticidal activity. By appropriate selection of rates and methods of application, therefore, the present compounds can be employed for these other utilities. For all of these uses, the compounds are employed in conventional manners.

Nematocidal Activity

The compound of Example 36 was expressly evaluated for the control of various nematode species. The compound was dissolved in 50:50 acetone:ethanol and diluted with water to create solutions of varying compound concentration. A 10 ml. aliquot of each solution was mixed well with one kilogram of moist nematode-infested soil, and the soil was then placed in pots and planted with crop seeds. The pots were held for a number of weeks, then the soil and roots were evaluated for the control of the nematode species. The crop was also evaluated for various effects of nematode damage.

In a first trial, the crop seeds were `Davis` soybean, the soil which was used was natural field soil heavily infested with two nematode species:

root-knot nematode (Meloidogyne incognita)

Race 3, cyst nematode (Heterodera glycines)

and also infested with three other nematode species:

stubby root nematode (Paratrichodorus christiei)

spiral nematode (Helicotylenchus dihystera)

lesion nematode (Pratylenchus brachyurus)

and the plants were allowed to develop for 9 weeks prior to evaluating the nematode control and effect on crop.

In the second trial, the crop seeds were `Rowden` cotton, the soil which was used was natural field soil infested with the following nematode species:

lesion nematode (Pratylenchus brachyurus)

stubby root nematode (Paratrichldorus christiei)

spiral nematode (Helicotylenchus dihystera)

lance nematode (Hoplolaimus galeatus)

and the plants were allowed to develop for 7 weeks prior to evaluating the nematode control and effect on crop.

In both tests, counts were also made of saprophagous nematodes.

Phenamiphos was employed as a reference standard in both trials. There were eight pots (replications) per treatment.

Results were as set forth in the following four tables.

                                      TABLE XVI                                    __________________________________________________________________________     Nematode/Soybean Trial/Nematode Ratings                                                       Number of       Number of                                                                              Number of                                              Root Knot                                                                               Number of                                                                             Spiral  Saprophagous                                           Nematodes                                                                               Stubby Root                                                                           Nematodes                                                                              Nematodes                                                                              Lesion                                          In      Nematodes                                                                             In      In      Nematodes                              Concentration                                                                           100 cc                                                                             From                                                                               In     100 cc                                                                             From                                                                               100 cc                                                                             From                                                                               From                            Treatment                                                                             Micrograms/ml                                                                           Soil                                                                               Roots                                                                              100 cc Soil                                                                           Soil                                                                               Roots                                                                              Soil                                                                               Roots                                                                              Roots                           __________________________________________________________________________     Example 36                                                                            1000     0   349 0      0   0   241 118 0                                      500      1   98  0      0   1   174 143 5                                      100      117 104 1      0   10  177 115 5                                      50       87  213 14     6   25  180 199 35                                     25       69  72  17     25  83  182 214 20                                      0                                                                                 Controls                                                                            62  134 53     31  129 216 245 20                                     0                                                                       Phenamiphos                                                                           1000     0   3   1      0   1    125                                                                               90  0                                      500      0   41  1      1   26  125 142 1                                      100      4   81  18     8   57  91  147 6                                      50       13  26  73     14  103 161 304 25                                     25       37  25  22     15  119 194 200 15                                      0                                                                                 Controls                                                                            26  30  53     35  252 222 249 37                                     0                                                                       __________________________________________________________________________

                                      TABLE XVII                                   __________________________________________________________________________     Nematode/Soybean Trial/Crop Ratings                                                                        Root                                                               Top Top Root                                                                               Condition    Gall Rate                                    Concentration                                                                           Height                                                                             Weight                                                                             Weight                                                                             (1-5, 1 = Best,                                                                        Gall (0-10, 0 = No                                                                            Cyst                        Treatment                                                                             Micrograms/ml                                                                           (cm)                                                                               (gms)                                                                              (gms)                                                                              5 = Worst)                                                                             Number                                                                              Galls, 10 = Worst)                                                                       Number                      __________________________________________________________________________     Example 36                                                                            1000     22.3                                                                               4.45                                                                               7.08                                                                               2.0     40   4.0       5                                  500      22.3                                                                               6.11                                                                               10.10                                                                              2.8     39   4.3       1                                  100      17.1                                                                               2.58                                                                               3.90                                                                               4.1     57   6.3       1                                  50       19.1                                                                               1.95                                                                               3.21                                                                               3.8     70   6.5       0                                  25       19.5                                                                               2.45                                                                               3.34                                                                               4.5     64   7.0       0                                   0                                                                                 Controls                                                                            19.1                                                                               2.06                                                                               3.06                                                                               4.8     70   6.6       0                                  0                                                                       Phenamiphos                                                                           1000     37.3                                                                               11.03                                                                              7.36                                                                               3.6     10   1.0       0                                  500      46.7                                                                               7.01                                                                               3.69                                                                               3.6      9   1.0       1                                  100      39.9                                                                               4.32                                                                               3.08                                                                               3.6     41   4.0       0                                  50       34.7                                                                               3.22                                                                               2.30                                                                               3.7     41   4.7       1                                  25       28.7                                                                               2.24                                                                               1.85                                                                               4.5     42   6.6       0                                   0                                                                                 Controls                                                                            23.2                                                                               2.72                                                                               3.35                                                                               4.2     55   5.8       0                                  0                                                                       __________________________________________________________________________

                                      TABLE XVIII                                  __________________________________________________________________________     Nematode/Cotton Trial/Nematode Ratings                                                  Number of      Number of                                                                              Number of      Number of                                Lesion  Number of                                                                             Spiral  Lance   Number of                                                                             Saprophagous                             Nematodes                                                                              Stubby Root                                                                           Nematodes                                                                              Nematodes                                                                              Dorylaimoid                                                                           Nematodes                       Treatment,                                                                              In      Nematodes                                                                             In      In      Nematodes                                                                             In                              Concentration                                                                           100 cc                                                                             From                                                                               In     100 cc                                                                             From                                                                               100 cc                                                                             From                                                                               In     100 cc                                                                             From                        Micrograms/ml                                                                           Soil                                                                               Roots                                                                              100 cc Soil                                                                           Soil                                                                               Roots                                                                              Soil                                                                               Roots                                                                              100 cc Soil                                                                           Soil                                                                               Roots                       __________________________________________________________________________     Example 36:                                                                    1000     0   1   0      0   1   5   --  8      122 48                          500      4   32  28     8   2   16  26  7      142 83                          100      24  260 91     9   9   34  61  4      189 89                          50       29  239 64     6   7   6   25  7      123 91                          25       38  321 69     10  4   15  20  16     141 124                             Controls                                                                            12  261 96     5   21  15  39  12     160 100                         Phenamiphos:                                                                   1000     0   4   12     2   5   3   6   3      71  25                          500      0   16  27     7   68  9   20  3      66  52                          100      4   61  55     16  202 23  33  3      133 148                         50       13  101 41     13  226 20  48  6      121 170                         25       19  181 65     17  217 33  57  9      137 204                             Controls                                                                            24  103 42     39  411 44  46  18     140 282                         __________________________________________________________________________

                                      TABLE XIX                                    __________________________________________________________________________     Nematode/Cotton Trial/Crop Ratings                                                                           Root                                                               Top Top Root                                                                               Condition                                                                              Gall Rate                                       Concentration                                                                             Height                                                                             Weight                                                                             Weight                                                                             (1-5, 1 = Best,                                                                        (0-10, 0 = No                                                                            Gall                           Treatment                                                                             Micrograms/ml                                                                             (cm)                                                                               (gms)                                                                              (gms)                                                                              5 = Worst)                                                                             Galls, 10 = Worst)                                                                       Number                         __________________________________________________________________________     Example 36                                                                            1000       10.7                                                                               1.33                                                                               0.91                                                                               3.5     0         0                                     500        10.9                                                                               1.22                                                                               0.75                                                                               3.9     0         0                                     100        11.6                                                                               1.27                                                                               0.76                                                                               3.3     0         0                                      50        11.4                                                                               1.24                                                                               0.63                                                                               4.2     0         0                                      25        11.3                                                                               1.26                                                                               0.78                                                                               4.0     0         0                                       0                                                                                  Controls                                                                            10.6                                                                               1.12                                                                               0.55                                                                               4.5     0         0                                      0                                                                      Phenamiphos                                                                           1000       12.8                                                                               1.45                                                                               0.85                                                                               3.2     0         0                                     500        14.8                                                                               1.76                                                                               0.98                                                                               3.3     0         1                                     100        14.8                                                                               1.72                                                                               0.75                                                                               3.7     0         0                                      50        14.6                                                                               1.71                                                                               0.77                                                                               3.8     0         0                                      25        14.6                                                                               1.60                                                                               0.71                                                                               3.9     0         1                                       0                                                                                  Controls                                                                            12.8                                                                               1.41                                                                               0.69                                                                               4.0     0         0                                      0                                                                      __________________________________________________________________________

Fungicidal Activity

Various of the compounds to be employed in accordance with the present invention were evaluated for the control of fungal and other plant pathogens. Each compound was formulated by dissolving it in a 1:1 mixture of acetone/ethanol with the aid of Tween 20 (an emulsifier sold by ICI Americas Inc.) and thereafter diluting the solution with water. The initial test concentration was 400 ppm; for some of the compounds, additional formulations were prepared containing lower concentrations of compound. A portion of the resulting formulation was sprayed onto the foliage of suitable plants, or onto a half of a grape in the case of Botrytis. The foliage or grape was subsequently infested with the pathogen, incubated where appropriate, and held for a period to permit expression of disease symptoms.

Activity against the pathogen was rated as follows:

1=0-19% disease control

2=20-29% disease control

3=30-39% disease control

4=40-59% disease control

5=60-74% disease control

6=75-89% disease control

7=90-96% disease control

8=97-99% disease control

9=100% disease control

0=no evaluation possible (too much injury)

Injury to plants was rated on a scale of 1-5, with 1=no injury and 5=death. However, this rating was recorded only when it was 2 or higher. The type of injury was additionally recorded in most ratings:

B=burning

C=chlorosis

G=general necrosis

S=stunting

The results are set forth in the following tables. Abbreviations have the following meanings:

Powd Mdew=Powdery Mildew

Rice Blst=Rice Blast

Leaf Rust=Leaf Rust

Botr Ytis=Botrytis

Appl Scab=Apple Scab

Dwny Mdew=Downy Mildew

Sept Oria=Septoria

Cerc Beet=Cercospora on Beet

                                      TABLE XX                                     __________________________________________________________________________     Foliar Applications                                                                     Powd                                                                               Rice                                                                               Leaf                                                                               Botr                                                                              Dwny                                                                               Appl                                                                               Sept                                                                               Cerc                                       Ex. No.                                                                             ppm Mdew                                                                               Blst                                                                               Rust                                                                               Ytis                                                                              Mdew                                                                               Scab                                                                               Oria                                                                               Beet                                       __________________________________________________________________________      1   400.00                                                                             1(4G)                                                                              0(4G)                                                                              0(4G)                                                                              8  0(5)                                                        400.00          1                                                              100.00          1      0(4G)                                                                              0(3G)                                               25.00           1                                                          4   400.00                                                                             0(4G)                                                                              0(4G)                                                                              0(4G)                                                                              9  0(5)                                                        400.00          9                                                              100.00          5      0(5)                                                                               0(3G)                                                                              0(5)                                            25.00           1                                                          5   400.00                                                                             5(2G)                                                                              0(3G)                                                                              0(3G)                                                                              1  8(3G)                                                       400.00             0(5)                                                        100.00             0(4G)                                                                              5   5   5(2G)                                           25.00              1                                                       6   400.00                                                                             1(3G)                                                                              0(5)                                                                               0(4G)                                                                              1  0(5)                                                    7   400.00                                                                             1   1   1(2G)                                                                              1  0(5)                                                    9   400.00                                                                             1   1   1   1  1                                                      10   400.00                                                                             1   1   3(2G)                                                                              1  1                                                      11   400.00                                                                             1   1   1   1  1                                                      13   400.00                                                                             0(4G)                                                                              0(5)                                                                               0(4G)                                                                              9  0(5)                                                        100.00                                                                             1(3G)                                                                              0(4G)                                                                              0(3G)                                                                              8  0(5)                                                                               0(5)                                                                               0(3G)                                               100.00      0(4G)                                                                              1                                                              25.00       9(3G)                                                                              1                                                              25.00       7(2G)                                                                              1                                                              6.25        3   1                                                              1.56        2   1                                                              400.00                                                                             0(5)                                                                               0(5)                                                                               0(4G)                                                                              8  0(5)                                                        25.00                                                                              1(2G)                                                                              0(4G)                                                                              8(2G)                                                                              1  0(5)                                                        6.25        8(2G)                                                                              1                                                         14   400.00                                                                             1   1   1   1  1                                                      15   400.00                                                                             1   1   1(2G)                                                                              1  1(3G)                                                  16   400.00                                                                             0(4G)                                                                              0(4G)                                                                              0(4G)                                                                              9  0(5)                                                        400.00          8                                                              100.00          1      0(4G)                                                                              0(3G)                                                                              0(4G)                                           25.00           1                                                         17   400.00                                                                             0(4G)                                                                              0(4G)                                                                              0(4G)                                                                              9  0(5)                                                        400.00          9                                                              100.00          1      0(4G)                                                                              0(3G)                                                                              0(5)                                            25.00           1                                                         18   400.00                                                                             3(2G)                                                                              0(3G)                                                                              7(3G)                                                                              1  0(5)                                                        400.00      7(3G)                                                              100.00      1          1   1   1                                               25.00       1                                                             19   400.00                                                                             5(2G)                                                                              0(3G)                                                                              0(3G)                                                                              1  0(5)                                                   20   400.00                                                                             1   1   1   1  0(5)                                                   21   400.00                                                                             7(4G)   0(4G)                                                                              7  0(5)                                                        100.00                                                                             6(3G)   0(3G)                                                                              1  0(5)                                                                               3   0(3G)                                                                              0(4G)                                           100.00      0(4G)                                                              25.00       0(3G)                                                              6.25        2(2G)                                                              400.00          1                                                              100.00          1      0(3G)                                                                              0(3G)                                                                              0(5)                                            25.00           1                                                              400.00                                                                             8(3G)                                                                              1   0(4G)                                                                              9  0(5)                                                        25.00                                                                              4(2C)   7(2G)                                                                              1  0(5)                                                        400.00                                                                             0(4G)                                                                              0(5)                                                                               0(4G)                                                                              9  0(5)                                                   23   400.00                                                                             1   1   1(2S)                                                                              1  0(5)                                                   25   400.00                                                                             0(3G)                                                                              0(5)                                                                               0(3G)                                                                              3  0(5)                                                   26   400.00                                                                             6(3G)                                                                              0(5)                                                                               0(4G)                                                                              1  0(5)                                                        100.00                                                                             4(3G)                                                                              0(4G)                                                                              0(3G)                                                                              1  0(5)                                                                               0(4G)                                                                              0(4G)                                               100.00      8(3G)                                                              25.00       6(2G)                                                              6.25        2                                                                  400.00                                                                             0(3G)                                                                              0(3G)                                                                              0(3G)                                                                              9  0(5)                                                        25.00                                                                              2(2G)                                                                              0(4G)                                                                              8(3G)                                                                              1  0(5)                                                   27   400.00                                                                             0(3G)                                                                              0(5)                                                                               0(4G)  0(5)                                                        100.00                                                                             2(2G)                                                                              0(3G)                                                                              0(3G)  0(5)                                                                               1(3G)                                                                              0(3G)                                               25.00       7(3G)                                                              6.25        2(2G)                                                              1.56        1                                                                  400.00                                                                             8(3G)                                                                              0(4G)                                                                              0(4G)                                                                              3  0(5)                                                        25.00                                                                              1   3(2G)                                                                              8(3G)  0(5)                                                   28   400.00                                                                             0(3G)                                                                              0(3G)                                                                              0(3G)                                                                              1  0(5)                                                   29   400.00                                                                             0(3G)                                                                              0(4G)                                                                              0(4G)                                                                              1  0(5)                                                   30   400.00                                                                             1(3G)                                                                              0(4G)                                                                              0(4G)                                                                              9  0(5)                                                        25.00           1                                                              400.00          8                                                              100.00          1      7(2G)                                                                              0(3G)                                                                              0(5)                                            100.00                 5(2G)                                                   25.00                  1                                                       6.25                   1                                                  32   400.00                                                                             1(3G)                                                                              0(5)                                                                               0(4G)                                                                              9  0(5)                                                        25.00           1                                                              400.00          9                                                              100.00          3      7(2G)                                                                              0(3G)                                                                              0(5)                                            100.00                 7(3G)                                                   25.00                  2                                                       6.25                   1                                                  34   400.00                                                                             4   1   7(3G)                                                                              1  0(5)                                                        25.00       2                                                                  400.00      0(3G)                                                              100.00      8(3G)          0(3G)                                               100.00      8(2G)      1   7(3G)                                                                              1(3G)                                           25.00       5(2G)          1                                                   6.25        2              1                                              36   400.00                                                                             7(3G)                                                                              0(4G)                                                                              0(4G)                                                                              7  0(5)                                                        25.00                                                                              1           1                                                              400.00                                                                             5(3G)       8                                                              100.00                                                                             3(2G)       2      7(3G)                                                                              3(2G)                                                                              0(4G)                                           100.00                 0(3G)                                                   25.00                  1                                                       6.25                   1                                                  37   400.00                                                                             0(4G)                                                                              0(5)                                                                               0(5)                                                                               9  0(5)                                                        400.00          8                                                              100.00          2  0(4G)                                                                              0(3G)                                                                              0(5)                                                25.00           1                                                         38   400.00                                                                             3   0(3G)                                                                              5(3G)                                                                              4  0(5)                                                   39   400.00                                                                             1   1   1   1  7(2G)                                                  40   400.00                                                                             9(3G)                                                                              0(4G)                                                                              0(3G)                                                                              1  0(5)                                                        100.00                                                                             8   0(3G)                                                                              7(2G)                                                                              1  0(5)                                                                               7(3C)                                                                              0(3G)                                                                              0(5)                                            100.00                                                                             7       9(3G)      0(3G)                                                   25.00                                                                              6       8(3G)      9                                                       25.00                                                                              4       8(2G)      8(2G)                                                   6.25                                                                               3       6(2G)      6                                                       1.56                                                                               1       5          3                                                       400.00                                                                             9(2G)                                                                              0(3G)                                                                              7(3G)                                                                              7  0(5)                                                        25.00                                                                              7   0(3G)                                                                              7(2G)                                                                              1  0(5)                                                        6.25                                                                               1       6          7                                                  41   400.00                                                                             0(3G)                                                                              0(4G)                                                                              0(3G)                                                                              1  0(4G)                                                  42   400.00                                                                             1   1   1   1  1                                                      43   400.00                                                                             1   1   1   1  1                                                      44   400.00                                                                             3(2G)                                                                              0(3G)                                                                              5(3G)                                                                              1  1                                                      45   400.00                                                                             1   7(2G)                                                                              5(2G)                                                                              1  8(2G)                                                       400.00  7          9                                                           100.00  3          2   1   1   1                                               25.00   2          1                                                      46   400.00                                                                             8   0(3G)                                                                              9(2G)  8(2G)                                                       100.00                                                                             8   0(3G)                                                                              9(2G)  8(2G)                                                                              3   1   0(5)                                            100.00                                                                             8   0(3G)                                                                              9(2G)  0(5)                                                        25.00                                                                              6   2(2G)                                                                              5(2C)  0(4G)                                                       6.25                                                                               5   1   2      1(2G)                                                       400.00                                                                             8   0(3G)                                                                              7(3G)                                                                              1  0(4G)                                                       25.00                                                                              6   7(2G)                                                                              9      1                                                      48   400.00                                                                             1(3G)                                                                              0(4G)                                                                              0(3G)                                                                              1  0(5)                                                   49   400.00                                                                             0(4G)                                                                              0(5)                                                                               0(4G)                                                                              7  0(5)                                                        400.00          1                                                              100.00          1      1(3G)                                                                              0(4G)                                                                              0(5)                                            25.00           1                                                         50   400.00                                                                             7   1   8   1  8(2G)                                                       400.00                                                                             1(3G)   0(4G)  0(5)                                                        100.00                                                                             1(2G)   8(3G)  0(4G)                                                                              1(2G)                                                                              0(3G)                                                                              0(3G)                                           25.00                                                                              1       2(2G)  1(2G)                                                  51   400.00                                                                             3(3G)                                                                              0(4G)                                                                              0(4G)                                                                              1  0(5)                                                   __________________________________________________________________________

Additional Fungicidal Testing

The compound of Example 46 was further evaluated for the control of various fungal pathogens. For these additional tests, the compound was formulated as described above for the general fungicidal testing. The compound was applied to foliage of a host plant, either before ("protective") or after ("curative") inoculation with the pathogen, while other applications were made as a soil drench. The host plant was wheat. Suitable reference standards, as well as a control, were used to verify each test. The results of these tests were as set forth in the following tables. Ratings were made on the same scales used in the previous table.

                  TABLE XXI                                                        ______________________________________                                         Wheat Powdery Mildew (Erysiphe graminis tritici)                                      Disease Ratings                                                                Rate  Foliar         Rate                                               Treatment                                                                               (ppm)   Protective                                                                               Curative                                                                              (lbs/acre)                                                                             Soil                                 ______________________________________                                         Compound of                                                                             400     7         5      10      1                                    Example 46                                                                              200     7         3      5       1                                             100     7         1      2.5     1                                              50     6         1                                                   ______________________________________                                    

                  TABLE XXII                                                       ______________________________________                                         Wheat Leaf Rust (Puccinia recondita tritici)                                              Foliar       Rate                                                   Treatment                                                                               Rate    Protective                                                                               Curative                                                                              (lbs/acre)                                                                             Soil                                 ______________________________________                                         Compound of                                                                             400     9(2G)     1(2G)  10      1                                    Example 46                                                                              200     9(2G)     1(2G)  5       1                                             100     9(2G)     1(2G)  2.5     1                                              50     8         1                                                   ______________________________________                                    

As will be apparent from the foregoing, many of the compounds of the present invention exhibit useful fungicidal activity. Accordingly, in another embodiment, the present invention is directed to a method of inhibiting a plant pathogenic fungal organism which comprises applying to a locus of the organism an inhibiting amount of a compound of the present invention. The method is practiced in accordance with standard techniques for the use of fungicides. The compounds can be formulated as described below in the Formulations section. In general, good fungicidal efficacy can be expected at rates of 0.5-5.0 lbs/acre.

Formulations

For any of their various uses, the compounds of the present invention are preferably formulated with a suitable agriculturally acceptable carrier. Typically such a formulation will contain from about 0.05 to about 95.0 percent by weight of the active ingredient. Examples of such compositions include sprayable formulations, such as wettable powders, aqueous suspensions and emulsifiable concentrates; and solid compositions, such as dusts, granules, and dry-flowable pellets. The compounds can also be formulated with fertilizer and applied to soil to achieve both a utility in accordance with the present invention as well as fertilization of the crop.

Sprayable formulations are in the form of concentrated compositions which can be diluted with water to form water dispersions or emulsions containing in the range from about 0.05 percent to about 10 percent of the active agent by weight. Such water dispersions or emulsions are sprayed onto plants or onto soil. The concentrated compositions may be either solids, usually known as wettable powders or dry flowables, or liquids, usually known as emulsifiable concentrates and aqueous suspensions.

A typical wettable powder comprises an intimate mixture of an active ingredient of the invention, an inert carrier, and surfactants. The concentration of the active agent is usually from about 25 percent to about 90 percent by weight. The inert carrier is usually chosen from among the attapulgite clays, the montmorillonite clays, the diatomaceous earths, the kaolinites, or the purified silicates. Effective surfactants, comprising from about 0.5 percent to about 10 percent by weight of the wettable powder, are chosen from among the condensed naphthalenesulfonates, the alkyl sulfates and the alkyl arylethoxylates. Suspending agents, such as the sulfonated lignins, can also be added.

A typical emulsifiable concentrate comprises from about 0.1 to about 6 pounds (from about 0.045 kg to about 3.05 kg) of a compound of the invention per gallon of liquid, dissolved in a mixture of organic solvents and emulsifiers. The organic solvent is chosen with regard to its solvency and its cost. Useful solvents include the aromatics, especially the xylenes and the heavy aromatic naphthas. Hydrophilic cosolvents such as DMF, cyclohexanone, and the glycol ethers such as 2methoxyethanol may be included. Other organic solvents may also be used, including the terpenic solvents and kerosene; methyl heptyl ketone and other high molecular weight ketones; cyclohexyl acetate and other high molecular weight esters. Suitable emulsifiers for emulsifiable concentrates are chosen from the alkylbenzenesulfonates, naphthalenesulfonates, and nonionic surfactants such as alkylphenol adducts of polyoxyethylene, and are used at similar percentages as for wettable powders.

An aqueous suspension, or flowable, is comprised of a finely ground suspension of the active ingredient dispersed in a water based system. This type of formulation is particularly useful for compounds with low water solubility. The concentration of active agent is usually from about 15 to 60 percent by weight. A typical aqueous suspension may comprise wetting and dispersing agents, antifreeze components, thickening or bulking agents, as well as water and the active ingredient.

Dust compositions containing a compound of the present invention usually contain from about 0.1 to about 50 percent by weight of the compound. Dusts are prepared by intimately mixing and finely grinding the active agent with an inert solid such as ground montmorillonite clay, attapulgite clay, talc, ground volcanic rock, kaolin clay, or other inert, relatively dense, inexpensive substances.

Solid, granular compositions are convenient for the application of compounds of this invention to the soil and will contain the active agent in an amount from about 0.1 to about 25 percent by weight. Granules comprise a compound of the invention dispersed on a granular inert carrier such as coarsely ground clay of from about 0.1 to about 3 mm particle size. The active ingredient is most conveniently applied to the clay by dissolving it in an inexpensive solvent, such as acetone, methylene chloride, xylene or other petroleum solvents, methoxy propylene glycol, or the like, and applying the solution to the sized clay in an appropriate solids mixer. The solvent is then typically removed by evaporation; however removal is not essential. Alternatively, any of the present compounds which is an oil can be sprayed, with or without heating, directly onto clay. Likewise, any of the present compounds which is a solid can be melted and then sprayed directly onto clay.

Representative formulations of the present invention are illustrated below.

Example A 10% Granule, Compound of Example 24

The compound of Example 24 was dissolved in acetone (in the ratio of 1 gram of compound per 4 grams of acetone). Propylene glycol was added and the mixture stirred, then poured over the carrier, mixed well, and air dried.

    ______________________________________                                         Ingredient       Percent by Weight                                             ______________________________________                                         Compound of Example 24                                                                          10                                                            Propylene glycol  5                                                            Florex 24/48 RVM 85                                                                             100                                                           ______________________________________                                          *RVM = regular volatile material                                         

EXAMPLE B 10% Granule, Compound of Example 1

The compound of Example 1 was dissolved in methylene chloride (a 12% solution), poured over the carrier, mixed well, and air dried.

    ______________________________________                                         Inqredient       Percent by Weight                                             ______________________________________                                         Compound of Example 1                                                                           10                                                            Florex 24/48 RVM 90                                                                             100                                                           ______________________________________                                    

EXAMPLE C 10% Granule, Compound of Example 36

The compound of Example 36 was formulated in the same procedure as the immediately preceding example.

    ______________________________________                                         Ingredient       Percent by Weight                                             ______________________________________                                         Compound of Example 36                                                                          10                                                            Florex 24/48 RVM 90                                                                             100                                                           ______________________________________                                    

EXAMPLE D 10% Granule, Compound of Example 37

The compound of Example 1 was dissolved in methylene chloride and an equimolar amount of tributylamine was slowly added to the solution to produce the salt of Example 37. The solution then containing the salt of Example 37 was poured over the carrier, mixed well, and air dried.

    ______________________________________                                         Ingredient       Percent by Weight                                             ______________________________________                                         Compound of Example 37                                                                          14.5                                                          Lowe's clay 30/40 mesh,                                                                         85.5                                                          Bloomfield, Missouri                                                                            100.0                                                         ______________________________________                                    

Examples E-H 10% Granule, Compound of Example 36

The procedure of the preceding example was used to make four 10% granular formulations from the compound of Example 1 and dimethylbis(C <-C s)ammonium chloride, the latter estimated to be only 75% pure, yielding formulations of the compound of Example 36. The four carriers were as follows:

Oil-Dri Mississippi Grey Clay

Oil-Dri Mississippi Brown Clay

Florex Clay LVM (low volatile material)

Lowe's Oran, Missouri Clay

The composition of all four formulations was as follows.

    ______________________________________                                         Ingredient       Percent by Weight                                             ______________________________________                                         Compound of Example 36                                                                          11.9                                                          Carrier          88.1                                                                           100.0                                                         ______________________________________                                    

Examples I and J 10% Granule, Compounds of Examples 1 and 36, Carrier Study

Various carriers were evaluated for 10% granular formulations of each of the compounds of Examples 1 and 36. Each compound was dissolved in dichloromethane, mixed, poured onto the respective carrier, mixed well, and air dried. The carriers evaluated were as follows.

Oil-Dri Mississippi Grey clay (this same clay is also referred to as Agsorb RVM-MS);

Oil-Dri Mississippi Brown clay (this same clay is also referred to as Agsorb LVM-MS);

Oil-Dri Georgia white clay--Oil Dry Corporation

Florex RVM;

Florex LVM--Floridin Company

Agsorb LVM--Oil Dry Corporation

Attapulgus RVM--Englehardt Minerals

Bentonite Granular--American Colloid

Pike's Peak clay (9-J)--General Reduction Crop.

KWK Volclay--American Colloid

Lowe's Oran, Missouri clay;

Lowe's Bloomfield, Missouri clay--Lowe's Industrial Products, Inc.

All formulations had the same composition:

    ______________________________________                                         Ingredient         Percent by Weight                                           ______________________________________                                         Compound of Example 1 or                                                                          10                                                          Example 36         90                                                          Carrier             100                                                        ______________________________________                                    

Based on the foregoing formulations, Oil-Dri Mississippi Grey clay and Oil-Dri Mississippi Brown clay are preferred carriers for the parent compounds, whereas Florex LVM clay and Lowe's Oran Missouri clay are preferred carriers for the salts.

Starting Materials

As taught above, th compounds of the present invention are prepared by the reaction of an acyl halide and an aniline, 1-aminonaphthalene, or 2-amino-5-nitropyridine: ##STR11## Theses starting materials are either known compounds or are prepared in known procedures. Essentially all of the anilines are known compounds. 1-Aminonaphthalene and 2-amino-5nitropyridine are likewise known compounds.

Some of the alkanoyl halides are known compounds. The following are described in the literature:

    ______________________________________                                          ##STR12##                                                                            Y            Reference                                                  ______________________________________                                                CN           A, B, C                                                           CF.sub.3     D, E                                                              n-C.sub.3 F.sub.7                                                                           F, G                                                       ______________________________________                                    

The following are also described in the literature:

(CF₃)₃ (CCOF--Reference D

(CF₃)₂ BrCCOF--Reference H

(CF₃)₂ ClCCOF--Reference I

(CF₃)₂ (CH₃)CCOF--Reference J

REFERENCES

A. U.S. 4,031,124 (1977)

B. U.S. 3,933,767 (1976)

C. U.S. 3,852,326 (1974)

D. U.S. 3,113,967 (1963)

E. J. Am. Chem. Soc., 84, 4275(1962)

F. U.S. 4,172,016 (1979)

G. J. F. Chem., 12 1-25 (1978)

H. Chem. Abs. 56, 312b (1961)

I. Tetrahedron, 27 3345-3355 (1971)

J. J. F. Chem., 29 471-474 (1985)

Other of the alkanoyl halide starting materials can be prepared in analogous manner.

In addition, most of the starting alkanoyl halides can be prepared by electrochemical fluorination of precursor non-fluorinated compounds:

    ______________________________________                                         Substituent on                                                                 present starting                                                                            Precursor                                                         material     substituent                                                                              Reference                                               ______________________________________                                         F            H         Hudlicky (following table)                              CF.sub.3     CH.sub.3  "                                                       C.sub.2 F.sub.5                                                                             C.sub.2 H.sub.5                                                                          "                                                       n-C.sub.3 F.sub.7                                                                           n-C.sub.3 H.sub.7                                                                        "                                                       OR.sub.f     OR        A                                                        ##STR13##   NR.sub.2  B, C, D                                                 ______________________________________                                    

Similarly, many of the alkanoyl halide starting materials are conveniently prepared by electrochemical fluorination of the precursors listed above, which are already partially fluorinated.

REFERENCES:

A. U.S. Pat. No. 2,594,272 (1952)

B. U.K. No. 666,733 (1952)

C. Chem. Abs., 65, 2140g (1966)

D. Chem. Abs., 62, 16089d (1965)

A general reference on electrochemical fluorination is "Chemistry of Organic Fluorine Compounds", by M. Hudlicky (Horwood Ltd., 1976), especially page 73. 

I claim
 1. A compound of formula I ##STR14## wherein R⁰ representsbromo, chloro, or fluoro; R¹ represents CF₃, C₂ F₅, C₃ F₇, or a n-, iso-, or sec-C₄ F₉ ; R² representsCF₃, C₂ F₅, or C₃ F₇, or, when R⁰ represents fluoro, R² can additionally represent--OR_(f), --N(R_(f))₂, --CN, 13 CF₂ --OR_(f), or --CF₂ --N(R_(f))₂ and each R_(f) independently represents perfluoroloweralkyl of C₁ -C₄ or, in --N(R_(f))₂ both R_(f) groups can be taken together with the N and constitute perfluoropyrrolidino, perfluoropiperidino, perfluoromorpholino, or N-(trifluoromethyl)perfluoropeiperazino; R³ representshydrogen, or methyl; and R⁴ represents5-nitro-2-pyridyl, thiocyanatophenyl bearing a single additional substitutent which is fluoro, chloro, bromo, iodo, or nitro, or substituted aryl of the formula ##STR15## wherein each R⁵ independently represents bromo, chloro, or fluoro; each R⁶ independently representsiodo, nitro, cyano, trifluoromethyl, fluorosulfonyl, methylsulfonyl, ethylsulfonyl, carbomethoxy, or carboethoxy; R⁷ representsmethyl, or, when two R⁶ moieties represent nitro at the 2-and 4-positions, R⁸ can additionally represent C₁ -C₄ alkoxy or C₁ -C₄ alkylthio located at only the 3- or 5-position; n represents 0-5; p represents 0-2 except that p can additionally represent 3 but only where two R⁶ moieties represent nitro and a third R⁶ moiety represents trifluoromethyl; q represents 0, or, when at least one R⁵, nitro, or fluorosulfonyl group is present, 1; r represents 0 or 1; and the sum of n, p, and q is: 2-5 when each of p, q, and r is 0; 2-3 when any one of p, q, or r is at least 1, except that when p is one and R⁶ is 4-nitro, the sum of n and p can additionally be 1;or a sodium, potassium, or ammonium salt of a foregoing compound, wherein ammonium is of the following formula ##STR16## wherein each R⁸ independently represents alkyl of C₁ -C₂₀, benzyl, 2-hydroxyethyl, 2-hydroxypropyl, or 3-hydroxypropyl; and R⁹ represents hydrogen or R⁸, the total number of carbon atoms in all R⁸ and R⁹ moieties being from 12 to 60, except that when one or more R⁸ groups are 2-hydroxyethyl, 2-hydroxypropyl, or 3™hydroxypropyl, the total number of carbon atoms in all R⁸ and R⁹ moieties can be from 6 to
 60. 2. A compound of claim 1 wherein R³ =H and R⁴ =2-F, -Cl, -Br, or -1-4-nitrophenyl or a salt thereof.
 3. A compound of claim 2 wherein R⁰ =F.
 4. A compound of claim 3 wherein R² =CF₃, C₂ F₅, or C₃ F₇.
 5. A compound of claim 5 which is 2'-bromo-4'-nitro-2,3,3,3-tetrafluoro-2-(trifluoromethyl)propionanilide or a salt thereof.
 6. A compound of claim 4 which is 2'-chloro-4'-nitro-2,3,3,3-tetrafluoro-2-(trifluoromethyl)propionanilide or a salt thereof.
 7. A compound of claim 4 which is 2'-iodo-4'-nitro-2,3,3,3-tetrafluoro-2-(trifluoromethyl)propionanilide or a salt thereof.
 8. A compound of claim 4 which is 2'-bromo-4'-nitro-2,3,3,4,4,4-hexafluoro-2-(trifluoromethyl)butyranilide or a salt thereof.
 9. A compound of claim 4 which is 2'-bromo-4'-nitro-2,3,3,4,4,4-hexafluoro-2-(pentafluoroethyl)butyranilide or a salt thereof.
 10. A compound of claim 4 which is 2'-bromo-4'-nitro-2,3,3,4,4,5,5,5-octafluoro-2-(trifluoromethyl)valeranilide or a salt thereof.
 11. A compound of claim 4 which is 2'-bromo-4'-nitro-2,3,3,4,4,5,5,5-octafluoro-2-(pentafluoroethyl)valeranilide or a salt thereof.
 12. A compound of claim 4 which is 2'-bromo-4'-nitro-2,3,3,4,4,5,5,5-octafluoro-2-(heptafluoropropyl)valeranilide or a salt thereof.
 13. A compound of claim 4, which is 2'-bromo-4'-nitro-2,3,3,4,4,5,5,6,6,6-decafluoro-2-(trifluoromethyl)hexananilide or a salt thereof.
 14. A compound of claim 4 which is 2'-bromo-4'-nitro-2,3,3,4,4,5,5,6,6,6-decafluoro-2-(pentafluoroethyl)hexananilide or a salt thereof.
 15. A compound of claim 3 wherein R² =OR_(f) or a salt thereof.
 16. A compound of claim 15 which is 2'-bromo-4'-nitro-2,3,3,3-tetrafluoro-2-(trifluoromethoxy)propionanilide or a salt thereof.
 17. A compound of claim 15 which is 2'-bromo-4'-nitro-2,3,3,3-tetrafluoro-2-(pentafluoroethoxy)propionanilide or a salt thereof.
 18. A compound of claim 15 which is 2'-bromo-4'-nitro-2,3,3,3-tetrafluoro-2-(heptafluoropropoxy)propionanilide or a salt thereof.
 19. A compound of claim 15 which is 2'-bromo-4'-nitro-2,3,3,3-tetrafluoro-2-(nonafluorobutoxy)propionanilide or a salt thereof.
 20. A compound of claim 3 wherein Rphu 2=--N(R_(f))₂ or a salt thereof.
 21. A compound of claim 20 which is 2'-bromo-4'-nitro-2,3,3,3-tetrafluoro-2-(octafluoromorpholino)propionanilide or a salt thereof.
 22. The compound of claim 1 which is 2',4'-dinitro-2,3,3,3-tetrafluoro-2-(trifluoromethyl)propionanilide or a salt thereof.
 23. The compound of claim 1 which is 2'-cyano-4'-nitro-2,3,3,3-tetrafluoro-2-(trifluoromethyl)propionanilide or a salt thereof.
 24. A compound of claim 1 which is 2'-(trifluoromethyl)-4'-nitro-2,3,3,3-tetrafluoro-2-(trifluoromethyl)propionanilide or a salt, thereof.
 25. A compound of claim 1 which is 2'-methyl-4'-nitro-2,3,3,3-tetrafluoro-2-(trifluoromethyl)propionanilide or a salt thereof
 26. A compound of claim 1 which is 2', 5'-dichloro-4'-nitro-2,3,3,3-tetrafluoro-2-(trifluoromethyl)propionanilide or a salt thereof.
 27. A compound of claim 1 which is 2',6'-dichloro-4'-nitro-2,3,3,3-tetrafluoro-2-(trifluoromethyl)propionanilide or a salt thereof.
 28. A compound of claim 1 which is 2'-methyl-4'-nitro-5'-chloro-2,3,3,3-tetrafluoro-2-(trifluoromethyl)propionanilide or a salt thereof.
 29. A compound of claim 1 wherein Ro represents chloro and both R¹ and R² represent trifluoromethyl.
 30. A method for inhibiting the growth of a plant which comprises applying to the plant an effective amount of an active agent which is a compound of claim
 1. 31. A method for inhibiting a plant pathogenic fungal organism which comprises applying to the locus of the orgauism an effective amount of an active agent which is a compound of claim
 1. 